A rapid, reliable and sensitive pressurized capillary electrochromatography-Laser induced fluorescence ( pCEC/LIF ) method with trifluoroacetic acid ( TFA ) pre-column derivation for simultaneous determination of four aflatoxin ( AFB1 , AFB2 , AFG1 , AFG2 ) was developed. This method included separation on a capillary column packed with 1. 8μm C18 particles using 0. 05% FA aqueous solution/methanol (55:45, V/V) as mobile phase at a pump flow rate of 0. 05 mL/min when the split ratio was 1:300. Under the optimum conditions including running voltage of 15 kV, excitation wavelength of 375 nm and emission wavelength of 450 nm, the baseline separation of four aflatoxins was achieved within 10 minutes. The limits of detection (LODs) were 0. 02, 0. 016, 0. 008 and 0. 01 μg/L for AFG1, AFB1, AFG2, AFB2(S/N=3), respectively. The linear detection ranges of AFG1 , AFB1 , AFG2 , AFB2 were 0. 1-10, 0. 1-10, 0. 1-3 and 0. 1-3 μg/L with correlation coefficients (R2) of 0. 9999, 1. 0000, 0. 9995 and 0. 9997, respectively. The established method was applied to analyze the peanut butter, and the recoveries of standard addition experiment were between 90 . 0% and 112 . 0% for all analytes ( RSDs=0 . 5%-1 . 9%) .