This study proposes a promising candidate for organic solar cells through the creation of a novel nano-hybrid system composed of caffeine molecules encapsulated within a semiconducting single-walled carbon nanotube known as NT14 (14,0). The stability and optoelectronic properties of this hybrid system, designated as CA@NT14, were thoroughly investigated. We determined the optimal diameter for the NT14 nanotube using molecular mechanics, Density Functional Theory, spectral moment's method, and bond polarizability model, finding it to be approximately 1.18 nm. The encapsulation's impact on the Raman-active modes, specifically the radial breathing mode and tangential mode, was analyzed through Raman spectra calculations, revealing structural stability and charge transfer from CA to NT14. Notably, the NT14's Fermi level position increased upon encapsulation, indicating charge transfer and a type-II band alignment. The study further examined the bandgap characteristics of the hybrid system, finding that the encapsulation of CA within semiconducting NT14 nanotubes minimally impacts the nanotube's bandgap, thus retaining its excellent visible light absorption properties. Conversely, encapsulating CA within metallic nanotubes significantly reduces their bandgap, limiting their light absorption range. The nonresonant Raman responses of NT14 pre-and post-encapsulation corroborated the charge transfer between CA and NT14. Future research will focus on computing the electronic transport characteristics, transmission spectra, I-V characteristics, and yield of CA@NT14 using DFT and Non-Equilibrium Green's Function ( formalism. An experimental study will be conducted to validate these theoretical findings. These results indicate the potential of CA@NT14 hybrids as effective active layers in organic solar cells, highlighting their significance in advancing optoelectronic applications.