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The promising functional tin oxide (SnO<i>_x</i>) has attracted tremendous attention due to its transparent and conductive properties. The stoichiometric composition of SnO<i>_x</i> can be described as common n-type SnO₂ and p-type Sn₃O₄. In this study, the functional SnO<i>_x</i> films were prepared successfully by plasma-enhanced atomic layer deposition (PEALD) at different substrate temperatures from 100 to 400 °C. The experimental results involving optical, structural, chemical, and electrical properties and morphologies are discussed. The SnO₂ and oxygen-deficient Sn₃O₄ phases coexisting in PEALD SnO<i>_x</i> films were found. The PEALD SnO<i>_x</i> films are composed of intrinsic oxygen vacancies with O-Sn⁴⁺ bonds and then transformed into a crystalline SnO₂ phase with increased substrate temperature, revealing a direct 3.5–4.0 eV band gap and 1.9–2.1 refractive index. Lower (<150 °C) and higher (>300 °C) substrate temperatures can cause precursor condensation and desorption, respectively, resulting in reduced film qualities. The proper composition ratio of O to Sn in PEALD SnO<i>_x</i> films near an estimated 1.74 suggests the highest mobility of 12.89 cm² V⁻¹ s⁻¹ at 300 °C.