A quintessential perspective for elaborating the pivotal role of quinary chalogenides such as CZTSSe plunges the thrust for exploration of non-vacuum approach for development of multicomponent chalcogenides utilizing organic surfactants and solvents for the nanocrystals ideal for photovoltaic applications. The piece of study envisages employment of TOPO-TOP as capping agents-cum-solvents for the very first time and have not been reported for CZTSSe-based materials till date. The work has been forwarded with the variation of anionic ratios in pristine counterparts of CZTSSe; i.e. CZTSe and CZTS in order to envision the potential of quinary chalcogenides wherein properties of two different materials coalesce to impart improved characteristics in CZTSSe. Varying Se:S ratios gradually during nanocrystals' synthesis by high-temperature colloidal route ensued precise control over the phase formation and morphology. With the employment of these capping agents, as-synthesized nanocrystals' are inherently Se-rich and high crystallinity restrains the need for selenization and high temperature annnealing respectively.