Optoelectronic devices have been developed using the polymer/fullerene nanocomposite, as focused in this review. The polymer/fullerene nanocomposite shows significant structural, electronics, optical, and useful physical properties in optoelectronics. Non-conducting and conducting polymeric nanocomposites have been applied in optoelectronics, such as light-emitting diodes, solar cells, and sensors. Inclusion of fullerene has further broadened the methodological application of the polymer/fullerene nanocomposite. The polymeric matrices and fullerene may have covalent or physical interactions for charge or electron transportation and superior optical features. Green systems have also been explored in optoelectronic devices; however, due to limited efforts, further design innovations are desirable in green optoelectronics. Nevertheless, the advantages and challenges of the green polymer/fullerene nanocomposite in optoelectronic devices yet need to be explored.