Prep the chicken: Trim and cut the chicken into 1- to 1.5-inch pieces.
Season lightly with salt and pepper.
Layer the base: Add chopped onion and bell peppers to the slow cooker. Scatter the minced garlic over top.
Add the chicken: Place the chicken pieces over the vegetables. Pour in the pineapple chunks and all the juice from the can.
Whisk the sauce: In a bowl, stir together ketchup, rice vinegar, soy sauce, and brown sugar.
Add red pepper flakes if using. Pour over the chicken and vegetables.
Cook low and slow: Cover and cook on Low for 4 to 5 hours or High for 2.5 to 3 hours, until the chicken is tender and cooked through.
Thicken the sauce: In the last 20 minutes, mix cornstarch with an equal amount of cold water to make a slurry. Stir it into the slow cooker.
Cover and cook until the sauce is glossy and thickened.
Taste and adjust: Add salt, a splash more vinegar for tang, or a pinch of sugar for sweetness if needed.
Serve: Spoon over hot rice. Top with sliced green onions or sesame seeds for a nice finish.