Pat the chicken breasts dry. If they are very thick, gently pound them to an even thickness.
Place the chicken in a shallow dish. Add olive oil, chili powder, smoked paprika, garlic powder, onion powder, salt, black pepper, and cayenne pepper.
Rub the seasoning evenly over both sides of the chicken. Let it sit for 10–15 minutes.
In a small bowl, whisk together honey, lime juice, chili sauce, Dijon mustard, and olive oil.
Reserve half of the glaze for serving and keep the other half separate for brushing onto the chicken during grilling.
Preheat the grill to 400–425°F (200–220°C) and lightly oil the grates.
Place the seasoned chicken on the grill and cook for approximately 5–7 minutes per side, depending on thickness.
During the final few minutes of grilling, brush the chicken with the peach glaze.
Continue cooking until the chicken reaches an internal temperature of 165°F (74°C).
While the chicken cooks, place the peach slices on the grill. Grill for 2–3 minutes per side, until tender with visible grill marks.
Transfer the chicken to a clean plate and let it rest for 5 minutes.
Top each chicken breast with grilled peaches.
Drizzle with the reserved glaze and garnish with fresh cilantro and lime wedges.
Serve immediately.