We performed an electrochromic investigation to optimize the composition of reactive magnetron-sputtered mixed layers of zinc oxide and tin oxide (ZnO-SnO2). Deposition experiments were conducted as a combinatorial material synthesis approach. The binary system for the samples of SnO2-ZnO represented the full composition range. The coloration efficiency (CE) was determined for the mixed oxide films with the simultaneous measurement of layer transmittance, in a conventional three-electrode configuration, and an electric current was applied by using organic propylene carbonate electrolyte cells. The optical parameters and composition were measured and mapped by using spectroscopic ellipsometry (SE). Scanning Electron Microscopy (SEM) and Energy-Dispersive X-ray Spectroscopy (EDS) measurements were carried out to check the SE results, for (TiO2-SnO2). Pure metal targets were placed separately from each other, and the indium–tin-oxide (ITO)-covered glass samples and Si-probes on a glass holder were moved under the two separated targets (Zn and Sn) in a reactive argon–oxygen (Ar-O2) gas mixture. This combinatorial process ensured that all the compositions (from 0 to 100%) were achieved in the same sputtering chamber after one sputtering preparation cycle. The CE data evaluated from the electro-optical measurements plotted against the composition displayed a characteristic maximum at around 29% ZnO. The accuracy of our combinatorial approach was 5%.