La1−xSrxMnO3 (LSMO) (x = 0−0.3) films were prepared on SrTiO3(001) substrates by the dipping-pyrolysis process using metal naphthenates as starting materials. Epitaxially grown LSMO films were obtained by heat treatment at 800–1200 °C; the fluctuation of alignment of these films, evaluated by reciprocal-space mapping of asymmetric x-ray diffraction, was markedly small, as comparable to that of the substrates. The LSMO films with x = 0.1−0.3 showed metallic conduction behavior at 25–300 K, and the resistivity was as low as that of LSMO single crystals, e.g., 4.5 × 10−4 Ω · cm at 150 K for the film with x = 0.3.