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Whisk together the peanut butter, water, tamari or soy sauce, vinegar, and 1/2 tablespoon of the sesame oil in a small bowl; set aside.
Heat the remaining 1 1/2 tablespoons oil in a large skillet or wok over medium-high heat until shimmering. Add the pork in a single layer, season with salt and pepper, and cook undisturbed until browned on the bottom, about 2 minutes minutes. Flip and continue cooking until all sides are browned and the pork is almost cooked through, about 2 minutes more.
Add the broccoli and cook, stirring occasionally, until just tender, about 4 minutes. Stir in the garlic and cook until fragrant, about 1 minute. Pour in the peanut sauce, stir to coat, and cook until the sauce thickens and is heated through, 1 to 2 minutes. Serve immediately over rice.