Cook rice per package directions.

Meanwhile, in a large skillet, bring 1/2 cup water to 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 1/2 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 1/4 cup water and cook, tossing, until coated in sauce, 30 seconds. Fold in broccoli. Serve over rice. Sprinkle with sesame seeds if desired.