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Combine chili powder, brown sugar, salt, onion powder, and black pepper in a small bowl. In a separate bowl, combine the barbecue sauce and chili sauce.
Add the onion and garlic to the bottom of a 6-quart slow cooker.
Dab the brisket dry with a paper towel and massage the spice rub over the surface of the brisket.
Add olive oil to a large skillet, over medium-high heat. Sear all edges of the brisket for about 1 minute per side.
Place the brisket on top of the onions and pour the sauce overtop.
Cook on low for 7 to 9 hours or until tender and internal temperature reads 205°F.
Optional broil: After the brisket is finished cooking, preheat the broiler to high (500°F). Line a rimmed baking sheet with foil and transfer the brisket to the baking sheet. Broil 6 inches from the heat for 4 to 6 minutes or until lightly charred.
Meanwhile, skim fat from the sauce/drippings. If you'd like to thicken the sauce, simmer it in a saucepan for about 5 minutes.
Let the brisket rest 10 minutes and then cut into thick slices across the grain. Serve with the reserved sauce or additional barbecue sauce.