Thirty-four sampling sites for surface water and twenty-seven sampling sites for ground water in areas of different land use were selected in the Wujiang River Basin, upstream section in Guizhou Province, China. Carbonic anhydrase (CA) activity in surface and ground water was analyzed and compared. The results show that CA activity was detected in all surface and ground water samples. In general, average CA activity in surface and ground water was highest from samples in arbor lands, followed by shrub lands, shrub and grass lands, agricultural lands, and residential areas. The average CA activity in ground water from arbor lands, shrub lands, and shrub and grass lands was higher than that in surface water. Water CA activity was positively correlated with HCO₃^- concentration in surface water and ground water. These results imply that the contribution of CA in water to the karst carbon sink potential of river basins warrants further extensive and in-depth research.