Crystalline Cu(In1-xGax)(3)Se-5 ingots, corresponding to the reported ordered vacancy compound (OVC), were grown by a horizontal Bridgman method. X-ray Lane back-reflection was performed on the as-grown surface of Cu(In1-xGax)(3)Se-5 ingots, showing the ingots to contain large single crystal regions. Hall effect measurements indicated that these materials have high electrical resistivity. Metallic Na was, for the first time, introduced into these materials to observe the doping effect using a sealed glass ampoule. Na can increase the carrier concentration significantly for the CuIn3Se5 material (x = 0) but does not have this effect on Cu(In1-xGax)(3)Se-5 materials (x > 0). Furthermore, in the present work, contrary to the reported data for thin film material, Na did not change the conductivity type of the Cu(In1-xGax)(3)Se-5 materials studied. Electron probe microanalysis (EPMA) showed that Na was detected only on the surface layer of the doped Cu(In1-xGax)(3)Se-5 samples. The electron generation mechanism in the CuIn3Se5 material due to the Na diffusion could be explained by defect generation related to Se and In sites.