Season chicken on both sides with salt and black pepper. In a large bowl, combine lemon juice, vinegar, peach preserves, mustard, cayenne, and 3 tablespoons oil.
Add chicken and turn to coat. Cover and let marinate at room temperature at least 30 minutes or up to 2 hours in the refrigerator.
Prepare a grill for medium-high heat; preheat 5 minutes. Grill chicken, turning halfway through, until charred and an instant-read thermometer inserted into thickest part registers 165°, about 6 minutes per side. Transfer to a platter.
Reduce grill to medium heat. Brush cut sides of peaches with remaining 1 tablespoon oil. Grill until charred, 3 to 4 minutes per side.
Arrange peaches around chicken. Top with basil.
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