Due to their excellent photoemissive properties, especially low thermal emittance and high sensitivity in the green wavelength, multi-alkali antimonide photocathodes, in particular, cesium–potassium–antimonide, emerged as prominent photoemissive materials for the electron sources of high-repetition-rate FEL applications. To explore its feasibility of operating in a high-gradient RF gun, DESY collaborated with INFN LASA to develop multi-alkali photocathode materials. In this report, we describe the recipe of K-Cs-Sb photocathodes, which were grown on a Mo substrate by varying the foundational Sb layer thickness using sequential deposition techniques. This report also illustrates the information regarding the film thickness, substrate temperature, deposition rate, and its possible effects on the photocathode’s properties. In addition, the influence of temperature on the cathode degradation is also summarized. Furthermore, in the framework of density functional theory (DFT), we investigated the electronic and optical properties of the K2CsSb material. The optical properties, such as dielectric function, reflectivity, refracting index, and extinction coefficient, were evaluated. The correlation between the calculated and measured optical properties, such as reflectivity, provides a better and more efficient strategy to rationalize and understand the photoemissive material’s properties.