A variety of junction capacitance-based characterization methods were used to investigate alloys of Ag into Cu(In1-xGax)Se2 photovoltaic solar cells over a broad range of compositions. Alloys show encouraging trends of increasing VOC with increasing Ag content, opening the possibility of wide-gap cells for use in tandem device applications. Drive level capacitance profiling (DLCP) has shown very low free carrier concentrations for all Ag-alloyed devices, in some cases less than 1014 cm−3, which is roughly an order of magnitude lower than that of CIGS devices. Transient photocapacitance spectroscopy has revealed very steep Urbach edges, with energies between 10 meV and 20 meV, in the Ag-alloyed samples. This is in general lower than the Urbach edges measured for standard CIGS samples and suggests a significantly lower degree of structural disorder.