FOR THE CRUST: – 1 1/2 vegetable shortening – 3 c. all-purpose flour, plus more for dusting – 1 large egg, beaten – 5 tbsp. ice water – 1 tbsp. distilled white vinegar – 1 tsp. kosher salt FOR THE FILLING: – 1 c. light corn syrup – 1 c. granulated sugar – 5 tbsp. salted butter, melted – 2 tbsp. packed light brown sugar – 1 tsp. vanilla extract – 1/2 tsp. kosher salt – 3 large eggs, beaten – 1 tbsp. unsweetened cocoa powder – 1 tbsp. plus 1 teaspoon ancho chile powder – 1/2 cayenne pepper – 1 1/4 c. pecan – 1 tbsp. powdered sugar
For the crust, combine shortening and flour in a large bowl with a pastry cutter for 3–4 minutes until coarse meal forms. Gently whisk in egg, cold water, vinegar, and salt.
Seal two even-sized dough balls in a large plastic bag. Roll each ball into a 1/2-inch disk with a pin. Seal bags and freeze 15 minutes. Thaw one frozen dough disk before using it (save the other for another pie).
For filling: In a large basin, mix corn syrup, granulated sugar, melted butter, brown sugar, vanilla, salt, and eggs. Add cocoa powder, 1 tablespoon ancho chili powder, and 1/4 teaspoon cayenne.
Stir the pecans with the powdered sugar, remaining 1 teaspoon ancho chile powder, and 1/4 teaspoon cayenne in a medium bowl until coated.
Put pecans equally in the pie crust. Pour corn syrup over pecans and spread evenly. Cover the pie with foil and bake for 40 minutes until the filling just sets.
Uncover the pie and bake for 40–50 minutes until firm but slightly jiggly. Allow it cool on a rack for 4 hours or overnight.