Spray cold grates of grill or grill pan with grilling spray and heat to medium. Pour balsamic vinaigrette into a large bowl. Grate about 1 teaspoon lemon zest into bowl and stir it into the dressing. Cut lemon in half.
Brush olive oil on bread slices. Grill peaches and bread slices just until lightly charred on each side, about a minute per side. Place lemons cut-side down on grill and cook until charred, about 2 minutes.
Gently stir grilled peaches and tomatoes into the balsamic vinaigrette. Arrange burrata on serving plate, breaking each ball open. Arrange tomatoes and peaches over burrata. Garnish your grilled peach, tomato, and burrata salad with lots of fresh herbs and pepitas and serve with the grilled lemons and grilled bread!