Solid-state electrolytes for Li-ion batteries are attracting growing interest as they allow building safer batteries, also using lithium-metal anodes. Here, we studied a compound in the lithium superionic conductor (LISICON) family, i.e. Li₄₋ₓGe₁₋ₓPₓO₄ (LGPO). Thin films were deposited via pulsed laser deposition, and their electrical properties were compared to those of ceramic pellets. A detailed characterization of their microstructures shows that thin films can be deposited fully crystalline at higher temperatures but also partially amorphous at room temperature. The conductivity is not strongly influenced by the presence of grain boundaries, exposure to air, or lithium deficiencies. First-principles molecular dynamics simulations were employed to calculate the lithium-ion diffusion profile and the conductivity at various temperatures of the ideal LGPO crystal. Simulations give the upper limit of conductivity for a defect-free crystal, which is in the range of 10–2 S cm–1 at 300 °C. The ease of thin-film fabrication and room-temperature Li-ion conductivity in the range of a few μS cm–1 make LGPO a very appealing electrolyte material for thin-film all-solid-state all-oxide microbatteries.