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Graphene (GN) and GN-based composites have perceived more attention due to their large surface area, excellent compatibility, low mass density, significant flexibility, as well as the exceptional synergistic effect of GN with inorganic/organic materials. Several studies have been carried out on the fabrication of GN/polymer nanocomposites (GPNCs) with novel and enhanced properties. However, several methods and chemical alterations have been used to efficiently disperse the GN within the polymer matrices for better performances and wider applications of the fabricated GPNCs. The present chapter begins with the introduction, historical background, and synthesis method of GPNCs. Moreover, modification techniques and interaction of GN with different polymers and their diverse applicabilities as biomedical, drug delivery, water purification, and sensors are discussed in brief.