Position a rack in the center of the oven and preheat to 350°F. Line a 12-cup muffin tin with paper liners and give them a light spray with nonstick cooking spray.
In a large bowl whisk together the whole wheat flour, cocoa powder, sugar, cinnamon, baking powder, baking soda, and salt until evenly combined and free of lumps.
Grate the zucchini on the large holes of a box grater. Wrap the shredded zucchini in a clean kitchen towel and squeeze over the sink until no more liquid comes out; measure 1 cup and transfer to a medium mixing bowl.
To the zucchini, add milk, eggs, melted butter, vanilla, and the orange zest. Whisk until smooth and uniform.
Make a well in the center of the dry ingredients and pour in the wet mixture. Using a flexible spatula, fold the batter gently until barely combined — a few streaks of flour are okay. Overmixing will make the muffins tough.
Fold the blueberries into the batter gently, reserving 8–10 berries to press on top of the muffins for a pretty finish.
Spoon the batter into the prepared cups, filling each about three-quarters full. Top with the reserved blueberries and, if you like, a sprinkle of turbinado sugar for sparkle.
Let the filled pan rest in the refrigerator for 8–10 minutes while the oven finishes heating; this brief chill helps the muffins rise evenly and results in a moister crumb.
Bake for 18–22 minutes at 350°F, rotating the pan once halfway through baking, until the tops spring back lightly and a toothpick inserted in the center comes out with a few moist crumbs but not wet batter.
Remove the pan to a wire rack and let the muffins cool in the tin for 5 minutes, then transfer the muffins to the rack to cool to warm or room temperature before serving.