MgZnO possesses a tunable bandgap and can be prepared at relatively low temperatures, making it suitable for developing optoelectronic devices. MgxZn1-xO (x~0.1) films were grown on sapphire by metal–organic vapor phase epitaxy under different substrate-growth temperatures Ts of 350–650 °C and studied by multiple characterization technologies like X-ray diffraction (XRD), spectroscopic ellipsometry (SE), Raman scattering, extended X-ray absorption fine structure (EXAFS), and first-principle calculations. The effects of Ts on the optical, structural, and surface properties of the Mg0.1Zn0.9O films were studied penetratively. An XRD peak of nearly 35° was produced from Mg0.1Zn0.9O (0002) diffraction, while a weak peak of ~36.5° indicated MgO phase separation. SE measurements and analysis determined the energy bandgaps in the 3.29–3.91 eV range, obeying a monotonically decreasing law with increasing Ts. The theoretical bandgap of 3.347 eV, consistent with the SE-reported value, demonstrated the reliability of the SE measurement. Temperature-dependent UV-excitation Raman scattering revealed 1LO phonon splitting and temperature dependency. Zn-O and Zn-Zn atomic bonding lengths were deduced from EXAFS. It was revealed that the surface Mg amount increased with the increase in Ts. These comprehensive studies provide valuable references for Mg0.1Zn0.9O and other advanced materials.