Preheat the air fryer to 400°F for 3 minutes. While it heats, place the sealed sauce packet in a bowl of hot tap water to thaw.
Add the frozen orange chicken pieces to the air fryer basket in a single layer.
Cook at 400°F for 10 minutes, shaking the basket at the 5-minute mark.
While the chicken cooks, toss the broccoli florets with the oil, salt, and pepper.
After 10 minutes, add the seasoned broccoli to the basket on top of and around the chicken.
Cook for another 6-8 minutes at 400°F, shaking once at the halfway point, until the chicken is golden brown and the broccoli is tender-crisp.
Transfer everything to a large bowl. Pour the thawed orange sauce over the top and toss gently to coat.
Garnish with sesame seeds and green onions. Serve immediately over rice.