Polymeric composite materials attracted attention when pristine polymers alone could not fulfill the necessity of high-performance functional materials for wide applications. Mixing two or more polymers (blends) together or compositing the polymers with inorganic compounds/carbon-based nanomaterials greatly solved the problem associated with the mechanical, thermal, and electronic properties along with the chemical stability, which paves a new pathway for optimizing the functional properties of active materials. However, a mere mixing of individual components sometimes would not provide enhanced properties due to the formation of phase-separated, larger domains of components. In particular, the grain boundaries of components, also known as “interfaces”, actually determine the properties of these composite materials. The tuning of interfacial properties is significant to achieve composites with higher electrical conductivity and better charge transfer kinetics if they are targeted toward high-performance energy devices. This review aims to provide an overview of recent advancements in the area of polymeric composite materials with tuned interfacial characteristics towards energy conversion (solar cells, photocatalytic hydrogen production, and nanogenerators) and energy storage (supercapacitors and metal-ion batteries) devices with very recent representative examples.