In this study, hollow fiber membrane extraction combined with ambient ionization mass spectrometry ( AMS) was developed for the simultaneous determination of 7 perfluorinated compounds ( PFCs) in aqueous solution, including perfluoroheptanoic acid ( PFHpA ) , perfluorooctanoic acid ( PFOA ) , perfluorooctane sulfonate acid ( PFOS ) , perfluorononanoic acid ( PFNA ) , perfluorodecanoic acid ( PFDA ) , perfluoroundecanoic acid ( PFUdA) , and perfluorododecanoic acid ( PFDoA) . PFCs were detected in negative ion mode using selective reaction monitoring ( SRM) mode. The extraction time and the pH value of extraction solution were optimized. 13 C4-PFOS and 13 C4-PFOA were used as internal standards for quantitative analysis. The method showed good linearity with correlation coefficient values ( r2 ) greater than 0. 991 for the seven target PFCs. With the exception of PFHpA, the limit of detection ( LOD) for other six PFCs was within ranges from 0. 8 to 2. 7 ng/L while the limit of quantitative (LOQ) was from 2. 7 ng/L to 8. 9 ng/L. The enrichment factor of five PFCs was more than two hundred. The developed method was applied to detect the seven PFCs in tap water and Pearl River water, and they were all not detected. The recoveries were within the ranges of 88. 5%-108. 3% and 94. 2%-116. 7% when 40 ng/L and 400 ng/L PFCs were spiked into tap water, respectively. In terms of the Pearl River water, the recoveries were within the ranges of 75. 0%-102. 6% and 81. 2%-97. 6% when 40 ng/L and 400 ng/L PFCs were spiked, respectively.