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Add onion, fresh pineapple chunks, soy sauce (*can substitute coconut aminos), rice wine vinegar, honey, sesame oil, garlic, five-spice powder, bell pepper, jalapeno pepper, and peanut butter to a 5 or 6-quart slow cooker crock. Stir to combine thoroughly.
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Heat olive oil in a large skillet over medium-high heat. Season trimmed pork roast on all sides with salt and pepper, to taste. Add to hot skillet and sear on all sides, approximately 2-3 minutes per side. Transfer seared pork to slow cooker crock.
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Reduce heat to medium and deglaze skillet with fresh pineapple juice. Use a spatula to scrape up flavorful brown bits from bottom of pan. Remove from heat and pour pan juices into the slow cooker.
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Cover and cook over high heat for 3-4 hours or low for 6-8. When finished, stir in fresh cilantro and transfer pork and pineapple mixture to a serving platter with a slotted spoon. Cover and keep warm.
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Optional: If desired, create a slurry by combining 2 tablespoons arrowroot and ¼ cup of juices from the slow cooker. Transfer remaining juices from the slow cooker to a large skillet over medium-high heat and whisk in the arrowroot slurry until well combined. Cook for several minutes or until sauce is reduced and thickened.
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To serve, spoon warm pork and pineapple mixture over a bed of cooked brown or cilantro-lime rice. Top with the juices or thickened sauce, if desired, and enjoy!