This study describes the construction of highly-sensitive photo-electrochemical (PEC) immunosensor for the detection of neuron-specific enolase (NSE). The biosensing platform is comprised of photo-active NiWO4 nanostructures, in-situ-grown over a conductive substrate (indium tin oxide) using a low-temperature template-based co-precipitation approach. The discussed approach enables the formation of discrete, yet morphologically-analogous, nanostructures with complete coverage (pinhole-free) of the electrode surface. The in-situ-grown nanostructure possess dense population with sharp saw-blade like morphological features that can support substantial immobilisation of anti-NSE agent. The constructed platform demonstrated excellent photo-catalytic activity towards uric acid (UA) which served as the base for the Electrochemical -mechanism (EC) based PEC inhibition sensing. The detection of NSE, relied on its obstruction in analytical signal observed for the photo-oxidation of UA after binding to the electrode surface via protein-antibody interaction. The constructed PEC immunosensor exhibits signal sensitivity up to 0.12 ng mL(-1) of NSE with excellent signal reproducibility and electrode replicability. Moreover, the constructed platform was successfully used for NSE determination in human serum samples.