Chemical processing of inorganic materials demands an understanding of the precursor chemistry at the molecular level. Although chemical compounds imitating atomic composition or bonding features of solid phases are efficient templates for a controlled evolution of nano-matter, the intrinsic advantages of this approach, such as atomic level mixing of the constituents and phase-selective synthesis, rely on the chemistry involved in the transformation of molecules to materials. Therefore, a better understanding of principles underlying chemical processing is necessary to enable a rational synthesis of materials. We have deposited MgAl2O4 thin films by the chemical vapor deposition of two Mg-Al alkoxide precursors, [MgAl2(OPri)8] and [MgAl2(OBut)8], which reveal that precursor attributes such as vapor pressure and ligand elimination mechanisms influence the microstructure and material properties of the spinel films. Under similar growth conditions, [MgAl2(OPri)8] produces rough and poorly crystalline spinel films, whereas crystalline deposits and dense microstructure were obtained in the case of [MgAl2(OBut)8]. The films were characterized by XRD, SEM, TEM, XPS and nano-indentation studies.