Laser‐driven physical vapor deposition (LDPVD) and radio‐frequency (rf) sputtering have been used to fabricate thin‐film solar cells on SnO2‐coated glass substrates. The laser‐ablation process readily permits the use of several target materials in the same vacuum chamber and complete solar cell structures have been fabricated on SnO2‐coated glass using LDPVD for the CdS, CdTe, and CdCl2. To date the best devices (∼9% AM1.5) have been obtained after a post‐deposition anneal at 400 °C. In addition, cells have been fabricated with the combination of LDPVD CdS, rf‐sputtered CdTe, and LDPVD CdCl2. The performance of these cells indicates considerable promise for the potential of rf sputtering for CdTe photovoltaic devices. The physical mechanisms of LDPVD have been studied by transient optical spectroscopy on the laser ablation plume. These measurements have shown that, e.g., Cd is predominantly in the neutral atomic state in the plume but with a large fraction which is highly excited internally (≥6 eV) and that the typical neutral Cd translational kinetic energies perpendicular to the target are 20 eV and greater. Quality of as‐grown and annealed films has been analyzed by optical absorption. Raman scattering, photoluminescence, electrical conductivity, Hall effect, x‐ray diffraction, and SEM/EDS.