This study examines the volatilization of alkali elements on the surfaces of ceramic targets and in the deposited films during the deposition of potassium sodium niobate (KNN) thin films using a ceramic target with the nominal composition K0.55Na0.55NbO3 via a RF magnetron sputtering process. Under a 100 W RF power condition, significant volatilization of alkali elements occurred on the surface of the ceramic target, resulting in the inevitable formation of a Nb-rich secondary phase in the thin films. However, perovskite-phase KNN thin films with excellent reproducibility and without secondary phases were obtained under 50 W RF power and a substrate temperature of 600 °C. When the RF power was reduced to 20 W or the substrate temperature was lowered to 500 °C under 50 W RF power, no crystalline thin films could be obtained. Additionally, when the substrate temperature was raised to 700 °C under 50 W RF power, the niobium-rich secondary phase appeared in the thin films due to the volatilization of alkali elements. The conditions of 50 W RF power and a substrate temperature of 600 °C were found to be optimal for depositing perovskite-phase KNN thin films. However, complete suppression of potassium volatilization from the thin films was not achievable. Consequently, the resulting films had a sodium-rich composition compared to K0.5Na0.5NbO3 and exhibited lower dielectric constants along with relaxor ferroelectric characteristics. This study highlights the importance of monitoring the compositional changes in ceramic targets during the RF sputtering process to ensure high reproducibility in KNN thin film fabrication.