Nature-inspired hierarchical architectures have recently drawn enormous interest in the materials science community, being considered as promising materials for the development of high-performance wearable electronic devices. Their highly dynamic interfacial interactions have opened new horizons towards the fabrication of sustainable sensing and energy storage materials with multifunctional properties. Nature-inspired assemblies can exhibit impressive properties including ultrahigh sensitivity, excellent energy density and coulombic efficiency behaviors as well as ultralong cycling stability and durability, which can be finely tuned and enhanced by controlling synergistic interfacial interactions between their individual components. This tutorial review article aims to address recent breakthroughs in the development of advanced Nature-inspired sensing and energy storage materials, with special emphasis on the influence of interfacial interactions over their improved properties.