Two low density organic solvents based liquid–liquid microextraction methods, namely Vortex assisted liquid–liquid microextraction based on solidification of floating organic droplet (VALLME-SFO) and Dispersive liquid–liquid microextraction based on solidification of floating organic droplet(DLLME-SFO) have been compared for the determination of multiclass analytes (pesticides, plasticizers, pharmaceuticals and personal care products) in river water samples by using liquid chromatography tandem mass spectrometry (LC–MS/MS). The effect of various experimental parameters on the efficiency of the two methods and their optimum values were studied with the aid of Central Composite Design (CCD) and Response Surface Methodology(RSM). Under optimal conditions, VALLME-SFO was validated in terms of limit of detection, limit of quantification, dynamic linearity range, determination of coefficient, enrichment factor and extraction recovery for which the respective values were (0.011–0.219ngmL−1), (0.035–0.723ngmL−1), (0.050–0.500ngmL−1), (R2=0.992–0.999), (40–56), (80–106%). However, when the DLLME-SFO method was validated under optimal conditions, the range of values of limit of detection, limit of quantification, dynamic linearity range, determination of coefficient, enrichment factor and extraction recovery were (0.025–0.377ngmL−1), (0.083–1.256ngmL−1), (0.100–1.000ngmL−1), (R2=0.990–0.999), (35–49), (69–98%) respectively. Interday and intraday precisions were calculated as percent relative standard deviation (%RSD) and the values were ≤15% for VALLME-SFO and DLLME-SFO methods. Both methods were successfully applied for determining multiclass analytes in river water samples.