Polyvinylpyrrolidone (PVP) is used in the synthesis of Ag nanoparticles (NPs) with controlled shape, most commonly producing cubes. The mechanism for shape control is unclear but believed by many to be caused by preferential binding of PVP to Ag(100) facets compared to Ag(111) facets and assumed by most to be the result of thermodynamic control, whereby facets with lower interfacial free energy predominate. To investigate this mechanism, we measured adsorption isotherms of PVP on different-shaped Ag NPs, to determine the thermodynamics of PVP adsorption to Ag(100) and Ag(111) facets. The equilibrium adsorption constant is independent of PVP molecular weight and depends only weakly on NP shape (and thus Ag facet). The equilibrium adsorption constant for PVP on Ag(111) (2.8 M-1) is about half that on Ag(100) (5 M-1). From a Wulff construction, this difference is not nearly enough to produce cubes via thermodynamic control. This result indicates the importance of kinetic control of the Ag nanoparticle shape by PVP, as has recently been proposed.