Remove as much fat as possible from chicken thighs. Place flour on a plate and roll chicken in flour, shaking off excess. Mix chicken broth, vinegar, five-spice powder, garlic, soy sauce and water together in a small bowl.
Heat oil in a wok or skillet over high heat until smoking. Brown chicken on all sides, about 2 minutes. Add sauce and lower heat to medium.
Simmer 25 minutes, turning chicken a few times. Liquid should be just at the bubbling stage. The sauce will boil down to a glaze. Serve over rice.