The effects of sample injection time, pH of the buffer solution, micelles concentration and micelles standing time on the peak splitting in MEKC were explored respectively in the research. 4-methyl phenethyl alcohol, 4-methoxy phenethyl alcohol, 4-nitro phenethyl alcohol, benzyl alcohol and phenethyl alcohol were selected as analytes and were separated by CE in a 50 μm i.d. × 60 cm (effective length 45 cm) fused-silica capillary at 20.0 kV. The buffer solution in MEKC consisted of 15.0 mM Na2B4O7, 10.0 mM NaH2PO4 and specific concentration of SDS. Suggestions to avoid the peak splitting were given. *