Solubilization efficiencies of naphthalene by micellar solution of a plant-based surfactant extracted from fruit of Sapindus mukorossi (reetha) and the synthetic surfactants like nonionic (Triton X-100 or TX-100), cationic (cetyltrimethylammonium bromide or CTAB), and anionic (sodium dodecylbenzenesulfonate or SDBS; dioctyl sodium sulfosuccinate or AOT; sodium octanesulfonate or SOS) in their single and as well as binary mixed (plant -synthetic) systems were measured and compared. The solubilization efficiency of single surfactants shows that reetha is less effective than TX-100, similar to SDBS, and more than AOT and SOS. The mixed surfactant systems show negative deviation in molar solubilization ratio (MSR) from ideality. The ascending order of percent change in MSR (Delta(MSR)) is TX-100-reetha < CTAB-reetha < SDBS-reetha < AOT-reetha < SOS-reetha. The mixed micellar solution for a particular combination also shows that Delta(MSR) is more negative when the interaction parameter for the mixed micelle (beta) is more negative. The results of this study may be useful for the applications of natural or natural -synthetic mixed surfactants in surfactant-enhanced remediation or detergency.