Redox electrolyte contacts offer a simple way of testing the photocurrent generation/collection efficiency in partially completed thin-film solar cells without the need to complete the entire fabrication process. However, the development of a reliable quantitative method can be complicated by the instability of the semiconductor/electrolyte interface. In the case of Cu(In,Ga)Se2 (CIGSe) solar cells, these problems can be overcome by using samples that have undergone the next processing step in solar cell fabrication, which involves chemical bath deposition of a thin (ca. 50 nm) CdS buffer layer. The choice of redox system is also critical. The frequently used Eu3+/2+ redox couple is not suitable for reliable performance predictions since it suffers from very slow electron transfer kinetics. This leads to the buildup of photogenerated electrons near the interface, resulting in electron-hole recombination. This effect, which can be seen in the transient photocurrent response, has been quantified using intensity-modulated photocurrent spectroscopy (IMPS). The study has demonstrated that the more oxidizing Fe(CN)63-/4- redox system can be used when a CdS buffer layer is deposited on the CIGSe absorber. The wide bandgap CdS acts as a barrier to hole injection, preventing decomposition of the CIGSe and formation of surface recombination centers. The IMPS response of this system shows that there is no recombination; i.e., electron scavenging is very rapid. It is shown that measurements of the external quantum efficiency made using the Fe(CN)63-/4- redox couple with CdS-coated CIGSe layers can provide reliable predictions of the short-circuit currents of the complete solar cells. Similar results have been obtained using CdS-coated GaAs layers, suggesting that the new approach may be widely applicable.