Alumina films with Im3 m, Ia3d, and onion-like mesopores have been synthesized using a single sol composition derived from an modified alumina precursor (MAP), partial acetylacetone (acac) chelated aluminum secondary butoxide (ASB/acac = 1:0.5). We observed that MAP undergoes oligomerization with aging time and the differently aged MAP generates different micellar structures in the presence of P123 in alumina sols and forms differently ordered mesostructured coatings. The time-dependent changes in the chemical nature of the MAP have been studied through ATR-FTIR spectroscopy. The nature of micellar transformations in the sols have been studied by transmission SAXS investigations. It has been observed that the size of the micelles gradually increases with time. On aging, MAP contains more bridging alkoxide groups with lesser hydrophilic characteristics; this reduces its interaction with the hydrophilic groups in the P123 micelle. Therefore, a mesostructure with low curvature is gradually formed in the sol due to the rigid nature of cross-linked MAP. Low angle XRD and TEM studies of the coatings obtained from the above sols have confirmed the generation of three distinctly different types of ordered mesoporous arrangements after heat treatments. The time-induced mesophase transformation mechanism has been proposed based upon the experimental results. The study reveals transformation of a modified Al alkoxide solution with respect to time and its successful use to obtain mesoporous alumina films of different ordered structures on glass.