The increasing global demand for sustainable energy has intensified the need for next-generation materials capable of efficient solar energy harvesting and storage. Here, we present a novel class of polymer-based functional materials designed for simultaneous high-efficiency solar energy conversion and integrated energy storage. By engineering the molecular architecture and incorporating multi-functional dopants, these materials exhibit enhanced light absorption, charge carrier mobility, and electrochemical stability under real-world operating conditions. The unique design allows photogenerated charges to be directly stored within the material matrix, effectively combining photovoltaic and supercapacitor functionalities into a single device. Experimental studies demonstrate a record-breaking energy conversion efficiency of 22.7% and stable energy retention over 1000 charge–discharge cycles. Advanced characterization techniques, including ultrafast spectroscopy and in situ electron microscopy, reveal the synergistic interactions between polymer chains and functional additives, which are crucial for maximizing performance. This work introduces a paradigm shift in the design of multifunctional polymeric materials, enabling scalable, lightweight, and flexible devices suitable for next-generation wearable electronics, autonomous sensors, and off-grid energy solutions. The proposed strategy not only addresses the critical challenges in conventional solar and storage systems but also opens new avenues for the rational design of integrated energy devices with unprecedented performance metrics. The presented research underscores the transformative potential of functional polymers in achieving sustainable and compact energy solutions, providing a roadmap for future innovation in solar-driven energy technologies.