Polyimide (PI) has emerged as a promising organic photocatalyst owing to its distinct advantages of high visible-light response, facile synthesis, molecularly tunable donor-acceptor structure, and excellent physicochemical stability. However, the synthesis of high-quality PI photoelectrode remains a challenge, and photoelectrochemical (PEC) water splitting for PI has been less studied. Herein, the synthesis of uniform PI photoelectrode films via a simple spin-coating method was reported, and their PEC properties were investigated using melamine as donor and various anhydrides as acceptors. The influence of the conjugate size of aromatic unit (phenyl, biphenyl, naphthalene, perylene) of electron acceptor on PEC performance were studied, where naphthalene-based PI photoelectrode exhibited the highest photocurrent response. This is resulted from the unification of wide-range light absorption, efficient charge separation and transport, and strong photooxidation capacity. This paper expands the material library of polymer films for PEC applications and contributes to the rational design of efficient polymer photoelectrodes.