Thermoelectricity offers a promising solution for reducing carbon emissions by efficiently converting waste heat into electrical energy. However, high-performance thermoelectric materials predominantly consist of rare, toxic, and costly inorganic compounds. Therefore, the development of alternating material systems for high-performance thermoelectric materials is crucial for broader applications. A significant challenge in this field is the strong interdependence of the various thermoelectric parameters, which complicates their simultaneous optimization. Consequently, the methods for decoupling these parameters are required. In this respect, composite technology has emerged as an effective strategy that leverages the advantages of diverse components to enhance the overall performance. After elaborating on the fundamental concepts of thermoelectricity and the challenges in enhancing the thermoelectric performance, the present review provides a comparative analysis of inorganic and organic materials and explores various methods for decoupling the thermoelectric parameters. In addition, the benefits of composite systems are emphasized and a range of low thermal conductivity materials with microporous to macroporous structures are introduced, highlighting their potential thermoelectric applications. Furthermore, the current development obstacles are discussed, and several cutting-edge studies are highlighted, with a focus on the role of high electrical conductivity fillers in enhancing the performance and mechanical properties. Finally, by combining low thermal conductivity materials with high electrical conductivity fillers can achieve superior thermoelectric performance. These insights are intended to guide future research and development in the field of organic porous materials and their nanohybrids in order to promote more sustainable and efficient energy solutions.