An ultrahigh-pressure cation exchanger dual on-line solid phase extraction/capillary reverse-phase liquid chromatography system are provided to maximize analysis efficiency of complicated biomaterial sample, to minimize dead time and to realize high reproducibility of retention time of the liquid chromatography. An ultrahigh-pressure cation exchanger dual on-line solid phase extraction/capillary reverse-phase liquid chromatography system comprises a sample inlet valve(100) including an inlet port(101) of strong cation exchange solvent, a sample inlet port(102), a sample outlet port(103), sample storage loop connection ports(104,104') and a column selection valve connection port(105); a column selection valve(200) which determines whether the inlet sample is transferred to the first column valve or to the second column valve, and includes a first column valve connection port(202) and a second column valve connection port(203); a first column valve(300) which is communicated with a first solid phase extraction column(302) and a first reverse-phase liquid chromatography column(303); a second column valve(400) which is communicated with a second solid phase extraction column(402) and a second reverse-phase liquid chromatography column(403); a solvent selection valve(500); a second solvent inlet valve(600); a second solvent supply pump; a first solvent supply pump; and a strong cation exchange solvent supply pump.
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