Self-assembly has the advantage of fabricating structures of complex functionalities, from molecular levels to as big as macroscopic levels. Natural self-assembly involves self-aggregation of one or more materials (organic and/or inorganic) into desired structures while templated self-assembly involves interstitial space filling of diverse nature entities into self-assembled ordered/disordered templates (both from molecular to macro levels). These artificial and engineered new-generation materials offer many advantages over their individual counterparts. This paper reviews and explores the advantages of such naturally self-assembled hybrid molecular level systems and template-assisted macro-/microstructures targeting simple and low-cost device-oriented fabrication techniques, structural flexibility, and a wide range of photonic applications.