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Trim fat from brisket. Cut brisket to fit into a 3-1/2- or 4-quart slow cooker. Place onion in the slow cooker. Combine chili powder, garlic powder, celery seeds and pepper in a small bowl. Sprinkle chili powder mixture evenly over meat; rub in with your fingers. Place meat in the slow cooker on top of onion.
Combine ketchup, chili sauce, brown sugar, vinegar, Worcestershire, liquid smoke, if using, and dry mustard in a medium bowl. Pour over brisket in cooker.
Cover and cook on Low for 9 to 10 hours or on High for 4 1/2 to 5 hours.
Remove brisket from cooker to a cutting board. Remove onion from cooker with a slotted spoon to a small bowl, reserving cooking juices. Skim fat off cooking juices; measure 3/4 cup of the juices. In a small saucepan, stir the cold water into flour; add the 3/4 cup cooking juices. Cook and stir over medium heat until thickened and bubbly; cook and stir for 1 minute more.
Thinly slice brisket across the grain. Place about 3 ounces cooked meat on each bun bottom. Top with onions and drizzle each with about 1 1/2 tablespoons sauce to serve.