In the quest to improve photoelectrochemical water-splitting performance, we have doped lanthanum (La) in highly crystalline zinc oxide (ZnO) nanorods (NRs) using a facile and low-temperature hydrothermal route and successful substitution of La3+ at the Zn2+ site is confirmed from structural and chemical analysis. The tapered NRs morphology gained after La doping resulted in lower optical bandgap of 3.17 eV, enhanced visible light trapping, and multiphoton absorption, which assist in achieving good PEC activity. The La doping also offered higher Urbach energy (EU), subsidizing the number of oxygen vacancies. The UPS spectra show that La doping reduces conduction band energy level and endorses smooth charge transportation. The La-doped ZnO exhibits two times enhancement in photocurrent (1.54 mA·cm−2) compared to pristine ZnO (0.81 mA·cm−2). The higher applied bias to the photon conversion efficiency of ∼1.14% for La-doped ZnO confirms the efficient utilization of solar energy. The EIS measurements demonstrated reduction in charge transfer resistance with La-doping. Mott-Schottky analysis shows that La doping lowers the flat-band potential and enhances charge transportation, making it a potential photoanode for PEC water-splitting applications.