Integration of chemical vapor deposited (CVD) graphene with textured‐Si substrates is an emerging research area wide open. Graphene can serve as both a transparent top electrode and a charge‐separating/transport‐active layer. However, its low light absorption capability, and high reflectance of planar‐Si substrate are major concerns for light harvesting required for photovoltaic devices especially solar cells and photodetectors (PDs). Therefore, CVD‐graphene/textured‐Si heterostructure effectively addresses this problem as the textured‐Si provides more surface area for light harvesting by suppressing light reflection and enables the efficient charge separation/transport as well. Recently, CVD‐graphene/textured‐Si Schottky junction based high performance solar cells and PDs have successfully been demonstrated. Moreover, the graphene coating on textured‐Si enhances the conductivity of Si anodes and provides structural stability for lithium‐ion batteries (LIBs). Furthermore, the optoelectronic coupled interfacial properties in such heterostructures suitably construct the platforms for surface enhanced Raman scattering (SERS) based detection and photocathodes for H2‐production, respectively. Hence, in this review, the fabrication of various CVD‐graphene/textured‐Si heterostructures and their applications in solar cells, PDs, SERS, LIBs, and H2‐production are critically analyzed with respect to the synergistic effect of Si‐texturing, electronic/optoelectronic properties of CVD‐graphene, etc. Finally, conclusions and outlook of this rapidly emerging and technologically broad research area are presented.