Poly(acrylamidoxime) adsorbents are often invoked in discussions of mining uranium from seawater. While the amidoxime-uranyl chelation mode has been established, a number of essential binding constants remain unclear. This is largely due to the wide range of conflicting pK(a) values that have been reported for the amidoxime functional group. To resolve this existing controversy we investigated the pK(a) values of the amidoxime functional group using a combination of experimental and computational methods. Experimentally, we used spectroscopic titrations to measure the pK(a) values of representative amidoximes, acetamidoxime, and benzamidoxime. Computationally, we report on the performance of several protocols for predicting the pK(a) values of aqueous oxoacids. Calculations carried out at the MP2 or M06-2X levels of theory combined with solvent effects calculated using the SMD model provide the best overall performance, with a root-mean-square deviation of 0.46 pK(a) units and 0.45 pK(a) units, respectively. Finally, we employ our two best methods to predict the pK(a) values of promising, uncharacterized amidoxime ligands, which provides a convenient means for screening suitable amidoxime monomers for future generations of poly(acrylamidoxime) adsorbents.