Co-doping represents a valid approach to maximize the performance of photocatalytic and photoelectrocatalytic semiconductors. Albeit theoretical predictions in hematite suggesting a bulk n-type doping and a surface p-type doping would deliver best results, hematite co-doping with coupled cations possessing low and high oxidation states has shown promising results. Herein, we report, for the first time, Sb and Li co-doping of hematite photoanodes. Particularly, this is also a seminal work for the introduction of the highly reactive Sb 5+ directly into the hematite thin films. Upon co-doping, we have a synergistic effect on the current densities with a 67-fold improvement over the standard. Via a combined investigation with profuse photoelectrochemical measurements, X-ray diffraction, X-ray photoelectron spectroscopy, and Raman analyses, we confirm the two doping roles of Sb 5+ and Li + as the substitutional and interstitial dopant, respectively. The improvements are attributed to a higher charge carrier concentration along with a lower charge transfer resistance at the surface.