Thin film batteries based on solid electrolytes having a garnet-structure like Li7La3Zr2O12 (LLZ) are considered as one option for safer batteries with increased power density. In this work we show the deposition of Ta- and Al-substituted LLZ thin films on stainless steel substrates by r.f. magnetron sputtering. The thin films were characterized by XRD, SEM and time-of-flight-secondary ion mass spectrometry (ToF-SIMS) to determine crystal structure, morphology and element distribution. The substrate temperature was identified to be one important parameter for the formation of cubic garnet-structured LLZ thin films. LLZ formation starts at around 650 °C. Single phase cubic thin films were obtained at substrate temperatures of 700 °C and higher. At these temperatures an interlayer is formed. Combination of SEM, ToF-SIMS and XRD indicated that this layer consists of γ-LiAlO2. The combined total ionic conductivity of the γ-LiAlO2 interlayer and the LLZ thin film (perpendicular to the plane) was determined to be 2.0 × 10−9 S cm−1 for the sample deposited at 700 °C. In-plane measurements showed a room temperature conductivity of 1.2 × 10−4 S cm−1 with an activation energy of 0.47 eV for the LLZ thin film.