The development of a simple but effective surface modification method is very important for the construction of biosensing interfaces. In this work, a postsynthetic water-soluble epinephrine-melanin (EPM) prepared from the self-polymerization of epinephrine has been demonstrated as an alternative of the widely used in situ formed polydopamine (PDA) for the surface coating of TiO2 nanoparticles and the construction of a photoelectrochemical (PEC) biosensing interface. In contrast to the formation of insoluble aggregates in solution for dopamine, a homogeneous solution was obtained for epinephrine after the self-polymerization. The use of EPM as a postsynthetic material enables the surface coating of TiO2 with the simple drop-casting method. Compared with the widely used dip-coating method for in situ PDA modification, the developed drop-casting method based on the use of water-soluble postsynthetic EPM saves more time, avoids the waste of bulk solution, and undoubtedly decreases the batch-to-batch inconsistencies. The simple coating of commercially available TiO2 nanoparticles with EPM greatly enhances the PEC performance due to the charge transfer property of EPM. The application of EPM in the construction of the PEC biosensing interface was demonstrated by the immobilization of a model biorecognition element (prostate specific antigen (PSA) antibody) onto EPM modified indium tin oxide (ITO) photoanode. Sensitive detection of PSA with high selectivity and stability was obtained on the basis of the biological recognition ability of PSA antibody. This work may renew the use of postsynthetic melanin-like biopolymers in other fields.