Recently, tungsten oxide (WO3) and bismuth vanadate (BiVO4) have been considered as an intriguing combination for constructing a heterojunction for efficient photoelectrochemical (PEC) applications. Herein, we report the preparation of ternary WO3/BiVO4/NiCo layered double hydroxide (LDH) photoanodes for boosting photogenerated carrier transport and promotion of catalytic activity. WO3/BiVO4 heterostructures were synthesized by a hydrothermal process of WO3 nanoplates on a fluorine-doped tin oxide (FTO) glass substrate, followed by spin-coating for BiVO4 materials. We investigated the effect of a NiCo LDH catalyst on PEC performance by controlling the growth temperatures of the NiCo LDH via hydrothermal synthesis. Moreover, the X-ray diffraction (XRD), Fourier‒transform infrared (FTIR) and X‒ray photoelectron spectroscopy (XPS) analyses revealed that the WO3/BiVO4 heterojunction was retained after the NiCo LDH growth process regardless of synthesis temperatures. The PEC results verified that the WO3/BiVO4 heterostructure with the optimized NiCo LDH catalyst (WBN60) possessed the best photocurrent density of 3.2 mA/cm2 at 1.23 V vs. reversible hydrogen electrode (RHE), which created improved charge separation and surface oxidation kinetics of photogenerated carriers. Consequentially, the smallest charge transfer resistance and recombination rate were achieved in the WBN60 electrode compared to others, indicating a much lower photoelectrode‒electrolyte interfacial resistance and the enhancement of photogenerated carrier transport by suppressing recombination.