Preheat oven to 325°F (170°C).: As the oven warms you will smell a neutral warmth, and preheating ensures the cake rises evenly from the moment it goes in. This temperature gives the Bundt enough time to bake through without overbrowning. A common error is skipping preheat, which leads to uneven texture, so always wait until your oven reaches the set temperature.
In a large bowl, whisk together granulated sugar, oil, banana, brown sugar, and peanut butter until well combined, about 1 minute. Add eggs and vanilla, and whisk until well combined. Whisk in buttermilk.: You will notice the mixture becoming glossy and uniform, with the peanut butter dispersing through the sweet base; the aroma becomes richer and slightly toasty. This step helps emulsify fats and liquids so your batter holds air for a tender crumb. Overmixing beyond this point can create excess gluten, so stop once smooth.
In a medium bowl, whisk together flour, baking powder, salt, and baking soda. Gradually whisk flour mixture into sugar mixture until just combined, stopping to scrape sides of bowl. (Do not overmix.): After adding the eggs the mixture will look more cohesive, slightly thicker and silkier, and you may hear a soft whisking sound as it comes together. Eggs bind and add structure while vanilla sharpens the profile. Avoid adding cold eggs straight from the fridge, as they can chill the batter and affect rise.
Spray a 10-cup Bundt pan with baking spray with flour. Pour batter into prepared pan. Tap pan on a kitchen towel-lined surface 4 to 5 times to settle batter and release any air bubbles.: When you pour in room temperature buttermilk the batter loosens and gains a gentle tang, smelling fresher and more balanced. This acid reacts later with the baking soda to aid lift. If you add cold buttermilk, the batter can seize and not blend smoothly, so bring it to room temperature first.
Bake until golden brown, a wooden pick inserted near center comes out clean, and an instant-read thermometer inserted near center registers 205°F (96°C), 50 to 55 minutes, covering with foil after 40 minutes of baking to prevent excess browning. Let cool in pan for 15 minutes. Invert cake onto a wire rack, and let cool completely.: Dry ingredients should be pale and powdery, and whisking them aerates the mix so the cake is lighter. This also ensures even distribution of leaveners to avoid tunnels or dense pockets. A common mistake is scooping flour directly with the measuring cup which packs it tight; spoon and level or weigh to prevent a dry, dense cake.
When ready to serve, spoon Chocolate Glaze on top of cooled cake.: You will see the batter thicken and take on a uniform, slightly glossy finish. The crumb develops when flour absorbs the liquids without overworking. Stir just until you no longer see streaks of flour, because overmixing develops gluten and makes the cake tough.
Spray a 10-cup Bundt pan with baking spray with flour.: Coating the pan prevents sticking and helps the cake release cleanly, which preserves the decorative shape. I tap the pan gently to spread the spray evenly so no pockets remain. Not preparing the pan well often results in chunks of cake left behind, so be thorough.
Pour batter into prepared pan.: As the batter flows into the pan you will hear a soft thump and see it level itself slightly; the surface will be glossy and thick. Pouring carefully avoids splattering and keeps the pan edges clean for a neat final presentation. Overfilling will cause spillover, so ensure your pan is the correct size.
Tap pan on a kitchen towel-lined surface 4 to 5 times to settle batter and release any air bubbles.: The gentle taps will quiet the batter and reveal any remaining air that might form large holes; the surface will smooth slightly. This step helps produce an even crumb and prevents big cavities. Be careful not to slam the pan hard, which can deflate too much air and make the cake heavy.
Bake until golden brown, a wooden pick inserted near center comes out clean, and an instant-read thermometer inserted near center registers 205°F (96°C), 50 to 55 minutes, covering with foil after 40 minutes of baking to prevent excess browning.: During baking the kitchen fills with a nutty, caramel scent and the top will become golden and set. Using an instant-read thermometer helps ensure the interior is fully cooked without overbaking. If you skip the foil and the top browns too quickly, tent it to avoid a bitter crust.
Let cool in pan for 15 minutes.: The cake will relax and slightly pull away from the pan walls, releasing steam and stabilizing the crumb; you will notice a softer scent and reduced steam as it cools. This rest prevents the cake from breaking when inverted. Trying to unmold while piping hot is a frequent mistake, causing the cake to crack or stick.
Invert cake onto a wire rack, and let cool completely.: As you flip the pan the cake should release smoothly with a satisfying sight of an intact silhouette; cooling on a rack prevents condensation underneath which keeps the crust tender. Full cooling is essential if you plan to glaze, because a warm cake will cause the glaze to slide off. Glazing too soon is a common misstep that ruins presentation.
When ready to serve, spoon Chocolate Glaze on top of cooled cake.: The glossy glaze will pool and highlight the Bundt ridges, adding a shiny contrast and deep chocolate aroma. Applying glaze slowly allows it to settle evenly and fill the crevices. If the glaze is too hot it will melt and run off, so cool it slightly before spooning.