In this paper, SnO(x) films were produced by reactive radio frequency magnetron sputtering under various oxygen partial pressure (P(O)) in conjunction with a thermal annealing at 200 °C afterwards. The obtained SnO(x) films were systematically studied by means of various techniques, including X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, spectroscopic ellipsometry, and Hall-effect measurement. The structural, chemical, and electrical evolution of the SnO(x) films was found to experience three stages: polycrystalline SnO phase dominated section with p-type conduction at P(O) ≤ 9.9%; amorphous SnO(2) phase dominated area at P(O) ≥ 12.3%, exhibiting n-type characteristics; and conductivity dilemma area in between the above mentioned sections, featuring the coexistence of SnO and SnO(2) phases with compatible and opposite contribution to the conductivity. The polycrystalline to amorphous film structure transition was ascribed to the enhanced crystallization temperature due to the perturbed structural disorder by incorporating Sn(4+) into the SnO matrix. The inversion from p-type to n-type conduction with P(O) variation is believed to result from the competition between the donor and acceptor generation process, i.e., the n-type behavior would be present if the donor effect is overwhelming, and vice versa. In addition, with increasing P(O), the refractive index decreased from 3.0 to 1.8 and the band gaps increased from 1.5 to 3.5 eV, respectively.