Doped ZnO are among the most attractive transparent conductive oxides for solar cells because they are relatively cheap, can be textured for light trapping, and readily produced for large-scale coatings. Here, we focus on the development of alternative Na and K-doped ZnO prepared by an easy low-cost spray pyrolysis method for conducting oxide application. To enhance the electrical properties of zinc oxide, alkali-doped Zn1−x MxO (x = 0.03) solid solutions were investigated. The resulting layers crystallize in a single hexagonal phase of wurtzite structure with preferred c-axis orientation along a (002) crystal plane. Dense, well attached to the substrate, homogeneous and highly transparent layers were obtained with great optical transmittance higher than 80%. The optical energy band gap of doped ZnO films increase from 3.27 to 3.29 eV by doping with Na and K, respectively. The electrical resistivity of the undoped ZnO could be decreased from 1.03 × 10−1 Ω.cm to 5.64 × 10−2 Ω.cm (K-doped) and 3.18 × 10−2 (Na-doped), respectively. Lastly, the carrier concentrations increased from 5.17 × 1017 (undoped ZnO) to 1 × 1018 (doped ZnO).