Preheat your oven to 350°F (175°C). Grease two 9-inch round cake pans with butter, line the bottoms with parchment paper, and butter the parchment. Dust the pans lightly with cocoa powder and tap out the excess.
In a large mixing bowl, whisk together the cake flour, sugar, cocoa powder, baking powder, baking soda, and salt until evenly combined.
In a separate bowl, whisk together the buttermilk, oil, eggs, and vanilla extract until smooth.
Pour the wet mixture into the bowl of dry ingredients and mix gently with a rubber spatula until mostly combined. Then slowly stir in the hot coffee. The batter will be thin. this is normal.
Divide the batter evenly between the prepared cake pans. Smooth the tops and bake for 25 to 30 minutes, or until a toothpick inserted in the center comes out clean. Let cakes cool in the pans on a wire rack for at least 1 hour.
In a stand mixer (or using a hand mixer), beat the butter and peanut butter on medium speed until creamy and fully combined, about 2 to 3 minutes.
Reduce the mixer to low and slowly add the powdered sugar, about ⅓ cup at a time. Scrape the sides of the bowl as needed. Mix in the vanilla extract and salt.
Add 2 tablespoons of buttermilk (or milk) and mix on low speed. Add an extra tablespoon if needed for a soft, spreadable texture. Beat on high for 30 seconds until light and fluffy.