Third order optical nonlinearities of various solvents such as Dimethylformamide (DMF), ethanol, chloroform, CCl4, acetone, toluene, Tetrahydrofuran (THF), and CS2 are studied in picosecond (ps) and femtosecond (fs) time scales using Z-scan technique. All the solvents show reverse saturable absorption behavior which is attributed to significant two-photon absorption and three-photon absorption processes in ps and fs time scale regimes, respectively. Nonlinear refraction studies reveal the positive signature of nonlinearity of solvents in both pulse regimes. We have investigated the effect of solvents on observed nonlinearities of near infra-red absorbing squaraine and croconate dye samples. Interestingly, a change in the sign of nonlinearity of molecules (phe cro, ptbu cro, phe squ, and ptbu squ) is observed in the ps regime when the solvent contribution is removed. Further, we also observed a change in magnitude of the nonlinearity for all the molecules under both pulse regimes. This gives clear evidence on the role of the solvents in the measurement of optical nonlinearities and that the true nonlinearities of the solute in fs/ps time domain can only be obtained when the measurements account for the solvent. © 2013 AIP Publishing LLC.