The present invention provides a method for measuring valproic acid and metabolites thereof, which comprises: (a) providing a sample including valproic acid or metabolites of valproic acid (b) extracting valproic acid or metabolites of valproic acid by a solvent to obtain an extract (c) providing an internal standard and adding to the extract (d) adding a derivatization reagent to the extract and heating to proceed derivatization to obtain a derivative solution including a product tagged with derivatization reagent and (e) using matrix-assisted laser desorption ionization and mass analyzer to analyze and determine the tagged product and calculating the amount of valproic acid or metabolites of valproic acid. The present invention further provides a system and a kit for measuring valproic acid and metabolites thereof.本發明提供一種量測丙戊酸及其代謝物的方法,其包含:(a)提供一含有丙戊酸或丙戊酸代謝物之樣本;(b)利用一溶劑萃取分離出該樣本中的丙戊酸或丙戊酸代謝物,以得到一萃取物;(c)提供一內部標準品,並加入該萃取物中;(d)將一衍生反應試劑加入該萃取物,並加熱進行衍生反應,以得到一含有具衍生反應試劑標記的產物之衍生溶液;及(e)利用基質輔助雷射脫附游離法及質量分析器以分析測定該具衍生反應試劑標記的產物,並計算丙戊酸或丙戊酸代謝物的含量。本發明另提供一種量測丙戊酸及其代謝物的系統及套組。