The establishment of charge transfer channels on BiVO photoanodes is a feasible strategy to achieve effective hole extraction and improve photoelectrochemical performance. Here, a conjugated polytrianiline framework (CPF-TTPATA) is proposed as a hole transport layer between the NiFeOx catalyst and the Mo:BiVO light absorber to improve the charge separation efficiency. The CPF-TTPATA features an acceptor triazine moiety linked by a donor triphenylamine moiety to accelerate the delocalization of photogenerated charges and possesses suitable band alignment with Mo:BiVO to form a staggered type-II heterojunction that facilitates hole extraction. Meanwhile, CPF-TTPATA passivates the surface trap states of Mo:BiVO, which promotes the interfacial charge transfer between Mo:BiVO and CPF-TTPATA. Therefore, the effective separation of photogenerated charge in our carefully designed Bi-acceptor-donor-catalyst conductive channel can be realized. The as-prepared NiFeOx/CPF-TTPATA/Mo:BiVO photoanode exhibits an extremely high photocurrent density of 6.94 mA cm and charge separation efficiency (≈100%) at 1.23 V (vs. RHE) under simulated AM 1.5G sunlight (100 mW cm). This work provides new insights for the design of organic and inorganic hybrid photoanodes for high-performance solar water splitting applications.