Prep the chicken. Pat the chicken pieces dry with paper towels.
In a bowl, toss with 1/2 cup cornstarch, salt, and pepper until evenly coated. Shake off excess so there’s a thin, even layer.
Whisk the sauce. In a measuring cup, whisk pineapple juice, vinegar, ketchup, brown sugar, soy sauce, and 1 tablespoon cornstarch until smooth. Set aside.
Sear the chicken. Heat 2 tablespoons oil in a large skillet over medium-high.
Add chicken in a single layer (work in batches). Cook 3–4 minutes per side until golden and just cooked through. Transfer to a plate.
Add more oil if the pan looks dry.
Stir-fry the vegetables. In the same pan, add peppers and onion with a pinch of salt. Cook 3–4 minutes, stirring, until crisp-tender and lightly browned at the edges.
Add aromatics and pineapple. Stir in garlic and ginger for 30 seconds until fragrant. Add pineapple chunks and toss for another minute.
Pour in the sauce. Give the sauce a quick whisk and add it to the pan.
Stir and let it bubble for 1–2 minutes until glossy and thickened.
Combine and finish. Return chicken and any juices to the pan. Toss to coat. Cook 1–2 more minutes to heat through.
Turn off heat and stir in sesame oil if using.
Serve. Spoon over hot rice. Sprinkle with sesame seeds and green onions. Taste and adjust with a splash more vinegar or a pinch of sugar as needed.