Place rack in the upper third of oven and preheat the oven to 350 degrees F. Lightly coat a a standard 12-cup muffin tins with cooking spray.
Sift the flour, sugar, cocoa, baking soda, baking powder, and salt into the bowl of an electric mixer fitted with a paddle attachment or a large mixing bowl. Mix on low speed until combined. In a separate medium bowl or large measuring cup, whisk together the buttermilk, oil, eggs, and vanilla. With the mixer on low speed, slowly pour the wet ingredients into the dry. With the mixer still on low, add the coffee and continue mixing, just until combined. The batter will be very thin.
Divide the batter evenly between the 12 muffin cups and bake 18 – 20 minutes, until a toothpick inserted in to the center of one cupcake comes out clean. Let the cupcakes cool in the pans for 20 minutes, then with a fork, gently lift them out onto a cooling rack to cool completely.
Prepare the ganache: Place the chocolate, heavy cream, and instant coffee in a heat-proof bowl over a pot of simmering water. Do not allow the water to boil or to touch the bottom of the bowl. Heat the chocolate, stirring often, until almost completely melted. Remove bowl from the sauce pan and stir gently with a rubber spatula until the chocolate is completely melted and the ganache is silky smooth.
While the ganache is still warm, spoon it over the top of each cupcake. While the ganache is still wet, sprinkle with fleur de sel. Let cupcakes sit a few moments to set, though ganache will not harden completely. Serve and enjoy.
Store leftover Salted Chocolate Olive Oil Cupcakes at room temperature for up to two days or in the refrigerator for up to five days. Although coffee is included in the batter and ganache, it adds moisture and intensifies the chocolate flavor. The cake, however, does not taste like coffee.
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