The chromatographic behavior of eight pesticides has been examined on cationic-micelles impregnated silica layers using mixed organic solvent (different combinations of hexane-acetone, v/v) systems. The chromatographic system constituting 0.01% CTAB (N-cetyl-N,N,N-trimethyl ammonium bromide) impregnated silica gel as stationary phase, and hexane-acetone in 1:1 ratio (v/v) as mobile phase was most favorable for on-plate identification of pesticides with preliminary separation. Surface modification of silica gel on impregnation, as indicated by SEM and FTIR studies was responsible for improved chromatographic performance. The results obtained on 0.01% CTAB impregnated silica layers were compared with those achieved on 0.01% CTAB impregnated kieselguhr, cellulose, or alumina layers. With selected chromatographic system, fivecomponent mixtures of pesticides (glyphosate, acephate, chlorpyrifos, malathion/methyl parathion, and isoproturon) were successfully resolved. The interference of metal cations as impurities on separation of pesticides from their mixtures was also examined. The developed method was successfully applied to the identification of pesticides in cereals, vegetables, and fruit grains. The applicability of the proposed method for the identification of five-component mixture of pesticides present in maize grains was also tested after separation on TLC plates. The limit of detection of glyphosate, acephate, chlorpyrifos, malathion, methyl parathion, and isoproturon was ≈20 µg per zone. For validation and reproducibility of the developed method, standard deviation (SD), ΔRF, and separation factor (α) were calculated.