A combined experimental and theoretical/band structure investigation is reported of Ga-doped CdO (CGO) and In-doped CdO (CIO) thin films grown on both amorphous glass and single-crystal MgO(100) substrates at 410 °C by metal-organic chemical vapor deposition (MOCVD). Film phase structure, microstructure, and electrical and optical properties are systematically investigated as a function of doping stoichiometry and growth conditions. XRD data reveal that all as-deposited CGO and CIO thin films are phase-pure and polycrystalline, with features assignable to a cubic CdO-type crystal structure. Epitaxial films grown on single-crystal MgO(100) exhibit biaxial, highly textured microstructures. These as-deposited CGO and CIO thin films exhibit excellent optical transparency, with an average transmittance of >80% in the visible range. Ga and in doping widens the optical band gap from 2.85 to 3.08 and 3.18 eV, respectively, via a Burstein-Moss shift. On MgO(100), room temperature thin film conductivities of 11 500 and 20 000 S/cm are obtained at an optimum Ga and in doping levels of 1.6% and 2.6%, respectively. Together, the experimental and theoretical results reveal that dopant ionic radius and electronic configuration have a significant influence on the CdO-based TCO structural, electronic, and optical properties: (1) lattice parameters contract as a function of dopant ionic radius in the order Y (1.09 Å) < in (0.94 Å) < Sc (0.89 Å), Ga (0.76 Å), with the smallest radius ion among the four dopants only shrinking the lattice marginally and exhibiting low doping efficiency; (2) carrier mobilities and doping efficiencies decrease in the order in > Y > Sc > Ga; (3) the Sc and Y dopant d states have substantial influence on the position and width of the s-based conduction band, which ultimately determines the intrinsic charge transport characteristics.