ITO/ZnO/CdS/CdTe/Mo solar cells have been grown in the substrate configuration by a combination of close-space sublimation and RF sputtering. A peak efficiency of 8.01% was achieved. A two stage CdCl2 annealing process was developed, with the first stage contributing to CdTe doping and the second being linked to CdTe/CdS interdiffusion by secondary ion mass spectrometry analysis. The inclusion of a ZnO layer between CdS and ITO layers improved performance significantly (from η=6% to η=8%) by increasing the shunt resistance, RSH, from 563 Ω cm2 to 881 Ω cm2. Cross-sectional scanning electron microscopy highlighted the importance of the resistive ZnO layer as numerous pinholes and voids exist in the CdS film. Solar cell performance was also investigated as a function of CdTe thickness, with optimal thicknesses being in the range 3–6 μm. All devices were deemed to be limited principally by a non-Ohmic back contact, the Schottky barrier height being determined to be 0.51 eV by temperature dependent J–V measurements. Modelling of device performance using SCAPS predicted efficiencies as high as 11.3% may be obtainable upon formation of an Ohmic back-contact. SCAPS modelling also demonstrated that a quasi-Ohmic back-contact may be achievable via inclusion of a highly p-doped (~1018 cm−3) buffer layer, between CdTe and Mo, which also has an optimal electron affinity (4.2 eV). The evaluation of device processing and the in-depth characterisation presented here provides a number of insights towards the continued improvement of substrate cell performance.