This review comprehensively addresses the developments and applications of polymer materials in optoelectronics. Especially, this review introduces how the materials absorb, emit, and transfer charges, including the exciton-vibrational coupling, nonradiative and radiative processes, Förster Resonance Energy Transfer (FRET), and energy dynamics. Furthermore, it outlines charge trapping and recombination in the materials and draws the corresponding practical implications. The following section focuses on the practical application of organic materials in optoelectronics devices and highlights the detailed structure, operational principle, and performance metrics of organic photovoltaic cells (OPVs), organic light-emitting diodes (OLEDs), organic photodetectors, and organic transistors in detail. Finally, this study underscores the transformative impact of organic materials on the evolution of optoelectronics, providing a comprehensive understanding of their properties, mechanisms, and diverse applications that contribute to advancing innovative technologies in the field.