Preheat the oven to 400°F (200°C). Lightly grease a 9×13-inch baking dish with nonstick cooking spray.
Arrange the chicken breasts in the prepared baking dish.
In a small bowl, whisk together the balsamic vinegar, honey, garlic, olive oil, Italian seasoning, salt, and black pepper.
Pour the sauce over the chicken, turning each breast to coat evenly.
Scatter the grape tomatoes around the chicken and place tomato slices on top of each breast.
Bake the Baked Caprese Chicken uncovered for 20–25 minutes, or until the chicken reaches an internal temperature of 165°F (74°C).
During the last 5 minutes of baking, place one slice of fresh mozzarella on each chicken breast.
For a golden, bubbly finish, broil on HIGH for 2–3 minutes.
Garnish generously with chopped fresh basil before serving.