Currently available methods for analyzing haloacetic acids (HAAs) and ketoacids in water generally require the use of diazomethane for sample derivatization. This article proposes methods based on a less toxic, alternative methylating agent. The objectives of this study were to develop and evaluate a liquid-liquid microextraction-acidic methanol derivatization procedure for HAA analysis and a microextraction-PFBHA-acidic methanol derivatization procedure for ketoacid analysis.