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Preheat oven to 350°F. In a small saucepan bring water and barley to boiling; reduce heat. Simmer, covered, for 8 minutes. Stir in fennel, sweet pepper, and onion. Cover and cook about 4 minutes more or until barley and vegetables are just tender. Remove from the heat; cover and set aside.
In a medium bowl whisk egg white until lightly beaten. Stir in 2 tablespoons of the Parmesan cheese, the bread crumbs, parsley, Italian seasoning, and black pepper. Add beef and mix well.
Lightly coat six 2 1/2-inch muffin cups with cooking spray. Divide beef mixture evenly among prepared cups. Press mixture on the bottom and up the sides of each cup, making a well in the center of each cup.
Drain barley mixture if needed. Spoon evenly into the wells in the beef cups. Cover top of pan with foil.
Bake for 10 minutes. Uncover and sprinkle tops with remaining Parmesan cheese. Bake, uncovered, for 3 to 5 minutes until the cups are heated through (160°F). Let cups cool on a wire rack for 5 minutes.
Run a thin sharp knife around the edge of each beef cup. Carefully remove cups from the pan. Divide cups between two serving plates. To serve, top with marinara sauce.