Abstract: Organic photovoltaic devices (OPVs) are emerging as a promising renewable energy source for the future. Their unique advantages, such as semitransparency, light weight, superior flexibility, and low cost, enable a wide range of applications. However, compared to silicon-based photovoltaics, OPVs still face challenges for further improving their efficiency. Additionally, there is a need to explore their potential of multi-functionality for practical application in various scenarios. This review summarizes the recent achievements in optimizing device performance and enhancing power-conversion efficiency, particularly via tuning the intermolecular interaction to reduce the electron-vibration coupling and non-radiative charge recombination (denoted as the “dilution effect”). Moreover, the representative development of ultra-thin Ag transparent electrode-based OPVs with multi-functional capabilities (such as semitransparency, flexibility, stretchability, and better aesthetics) have also been covered. Therefore, this review aims to provide a broad landscape on the recent development of OPV and to unlock the full potential of OPVs .