This article reviews the successive development of photo-assisted electrochemical performances using functionalized polymer materials. The photoelectrochemical technologies have already been well-established as a major tool for generating renewable energy harvesting solar power. In this regard, the research on the generation of new photoactive polymer supported units has drawn remarkable attention to improve the power conversion output and build up low-cost advanced devices. So, starting from fundamental working principle, we have tried to overview comprehensively the key features of most of these studies, which involve the tactical schemes behind the appropriate selection of different substituents to functionalize the polymer skeleton to achieve an optimal bandgap, challenges faced specially in the index of performance in post synthetic phase, the possible routes to overcome the hurdle, so that it can harvest photons matched with the solar spectrum and of course their relevance in the broad range of application window. Apart from photovoltaic solar cell application, the idea has been logically extended to cover highly selective photoelectrochemical sensing devices,where we have disclosed briefly the role of polymers in designing innovative biosensors, the trend of development along with specific illustrative examples, and some of their successful utilization in real time assay. The overall description is entirely focused on how these strategies have emerged from the background concepts and finally shaped to a viable and significant outcome.