A　high-performance　CE　with　amperometric　detection　(CE-AD)　was　employed　for　the　kinetic　study　of　keto-enol　tautomerism　of　p-hydroxyphenylpyruvic　acid　(pHPP).　Several　factors　(concentration　of　β-cyclodextrin　(β-CD),　concentration　and　pH　of　running　buffer,　separation　voltage　and　injection　time)　affecting　CE-AD　were　investigated　and　separation　conditions　were　optimized.　The　kinetics　of　pHPP　was　performed　in　water　solution　and　phosphate　solution　under　different　pH　and　temperature,　the　homologous　ketonization　rate　constants　and　half-life　were　obtained.　Also,　the　activation　energy　was　calculated　according　to　the　rate　constants　under　different　temperature.　The　experimental　results　indicated　that　β-CD　played　an　important　role　in　the　separation,　therefore　UV　spectrometric　method　was　applied　for　the　study　of　complexation　interaction　between　ketonic　pHPP　and　β-CD.　The　results　indicated　that　the　stoichiometric　ratio　of　the　pHPP-β-CD　complex　was　1:1　and　formation　constant　was　determined.　The　obtained　kinetic　results　are　in　correspondence　with　those　reported　by　our　group　with　CE-UV.　©　2009　Wiley-VCH　Verlag　GmbH　&　Co.　KGaA.