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Adjust oven rack to middle position and preheat oven to 350°F (175°C). Using baking spray, grease Bundt pan.
In a medium saucepan, combine butter, cocoa powder, espresso powder, and water. Bring to a boil over medium-high heat, stirring with a heat-proof flexible spatula, until mixture is homogeneous, about 2 minutes.
In a large bowl, whisk flour, brown sugar, baking powder, baking soda, and salt to combine.
Whisk in cocoa mixture, followed by bananas, sour cream, eggs, and vanilla, until smooth.
Using a flexible spatula, fold in walnuts.
Scrape batter into prepared pan and bake until tester inserted in center of cake comes out clean, about 75 minutes.
Transfer cake to cooling rack and cool 10 minutes, then invert directly onto rack and cool to room temperature, about 1 hour.
Sprinkle with confectioners’ sugar using a fine-mesh strainer and serve.