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Cook rice per package directions.
Meanwhile, in a large skillet, bring ½ cup water a simmer on medium. Add broccoli and cook, covered, until bright green and barely tender, 4 to 5 minutes. Transfer broccoli to plate and wipe out skillet.
In medium bowl, toss steak, five-spice powder, and ½ teaspoon each salt and pepper to coat. Add 1 tablespoon canola oil to skillet and heat on medium-high. In batches, cook steak in single layer until browned, 2 minutes per side. Transfer to bowl.
Reduce heat to medium, add remaining tablespoon oil to skillet, then chili black bean paste and cook, stirring, until fragrant, 1 minute. Return steak and any juices to skillet along with ¼ cup water and cook, tossing, until coated in sauce, 30 seconds. Fold in broccoli. Serve over rice. Sprinkle with sesame seeds if desired.