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Use a fork to whisk the cornstarch and water together in a small bowl. It will be a thick, milky liquid.
Combine the cornstarch mixture, brown sugar, honey, soy sauce, vinegar, garlic, ginger, and pepper in a small saucepan over low heat.
Whisking occasionally, bring to a boil. Once boiling, stop whisking and allow to boil for 2 minutes, or until the sauce coats the back of a spoon and is the consistency of maple syrup.
Turn off the heat and set aside for at least 10 minutes, allowing it to cool and thicken.
Meanwhile, preheat oven to 400°F (204°C). Lightly grease a 2–3-quart baking dish.
Pat the chicken dry with paper towels. Arrange in the prepared pan. Add the pineapples on top and all around the chicken.
Pour sauce on top, then turn the chicken over to make sure every inch is coated in the sauce.
Bake uncovered for 30–32 minutes or until the chicken is completely cooked through (internal temperature should be at least 165°F (74°C)).
This is optional: at the 25-minute mark, remove from the oven and carefully slice the chicken into chunks, then return to the oven.
Sprinkle green onion and sesame seeds on top and serve the chicken and pineapple with sauce from the pan poured on top.