A new derivatization reagent, 2,3,4,5,6-pentafluorobenzyl bromide (PFBBr), was employed to determine seven perfluoroalkyl carboxylic acids (PFCAs) simultaneously in tap water with gas chromatography-mass spectrometry (GC-MS) technique in this study. Firstly, seven PFCAs were derivatized to their corresponding esters under alkaline condition. The derivatization conditions including the amount of PFBBr and K₂CO₃, derivatization temperature and time were optimized to increase the derivatization efficiency. The 14 tap water samples collected from different places of China were enriched and purified through solid phase extraction pretreatment. The limits of detection (LODs) and the limits of quantitation (LOQs) ranged from 0.1 ng/L to 0.28 ng/L and from 0.3 ng/L to 0.84 ng/L, respectively. The new method offers a linear relationship in the range from 2 ng/L to 2000 ng/L, and the correlation coefficients ranged from 0.9938 to 0.9994. The results showed that GC-MS combined with pre-column derivatization is a reliable method for the analysis of PFCAs in the aqueous environment.