Metal-ion doping and halogen substitution have been largely applied to tune the bandgap of bismuth oxybromide (BiOBr) to upgrade its photodegradation capacity. In this work, the adsorption capacity and photocatalytic behavior of solvothermally synthesized BiOBr photocatalysts can be optimized via the synergistic effect of Y3+- and I--doping. After an adsorption reaction in the dark and exposure for another 80 min to visible light, pure BiOBr can remove 46.5% of Congo red (CR) from water with an initial CR concentration of 50 mg L-1. Meanwhile, Bi0.8Y0.20OBr0.97I0.03, the co-doped catalyst, displays total degradation rates exceeding 98% and 92% with CR dosages of 50 and 100 mg L-1, respectively, demonstrating a doubled degradation capacity. With the co-doping solution, the negative charges on the catalysts reduce, more oxygen vacancies are generated, the bandgap remarkably narrows, and the photoabsorption range broadens for derivation of photoinduced electron-hole pairs. The mechanism for optimized photodegradation behavior and dramatically increased adsorption capacity are discussed based on analyses of the structural evolution, surface properties including the chemical state and surface charge, electrochemical performance and the yield/type of photogenerated species. Density functional theory (DFT) simulations were conducted to investigate the structural state, density of states (DOS) and electrostatic potential.