Rapid technological advancements in flexible nanoelectronics have fueled the need for high‐performance materials with advanced structural architectures and superior properties. In this regard, conducting polymer nanocomposites are at the forefront of current innovative research owing to their excellent properties. Among these sets of unique materials, poly(3,4‐ethylenedioxythiophene)‐poly(styrenesulfonic acid) (PEDOT:PSS) nanocomposites continue to pave the way in several applications including those entailing thermoelectricity, transparent electrodes, photovoltaics, technical coatings, lighting, sensing, bioelectronics, hole transport layers, interconnectors, electroactive layers, and motion‐sensing conductors. The versatility and intriguing properties of these composites, particularly with 2D nanomaterials, have garnered significant attention from academia as well as industry. Therefore, in this review, the latest developments in PEDOT:PSS nanocomposites with graphene and its derivatives are focused on. First, the synthesis and fabrication of PEDOT:PSS nanocomposites with emphasis on recent techniques developed to overcome the challenges associated with direct production is discussed. Thereafter, the characterization and thermoelectric properties of the materials are explained. This provides detailed insights into the characteristic features of various nanocomposites and the influence of individual nanoparticles in the PEDOT:PSS matrix. Then, a conclusion, including a critical summary of the extensive applications of the PEDOT:PSS/graphene nanocomposites for electrochemical, electrostatic, optoelectronic, and thermoelectric devices, is provided.