Electropositive elements are often adsorbed on metals to produce a well-known decrease in the surface work function. During deposition, the work function drops steeply and reaches a minimum at coverage lower than one monolayer. Then, it increases slightly and the work function converges to the value of the deposited element. In this work, we report anomalous behavior found during the deposition of barium on a Ag(111) surface. After a minimum of about 2.4 eV the work function did not increase up to 2.7 eV, the bulk barium work function, no matter what amount of barium was deposited. Auger electron spectroscopy corroborated these results in which we measured a permanent and constant intensity of,the Ag MNN peak for high barium coverage. To explain this anomalous growth of barium on Ag(111) we propose an explanation based on the diffusion of silver atoms into the barium film. Further experiments showed that coadsorption of oxygen before a second deposition of barium blocked the diffusion, thus allowing the work function to reach 2.7 eV.