© 2021, The Minerals, Metals & Materials Society and ASM International.The effects of amorphous structure on the devitrification of Al90Tb10 marginal glass former system were investigated in detail by a combined study of high-energy X-ray diffraction (HEXRD), X-ray absorption fine structure (EXAFS), reverse Monte Carlo simulations (RMC), transmission electron microscopy (TEM) and thermal analyses. The atomic structures of melt-spun ribbons and magnetron sputtered amorphous samples with the same composition were simulated using RMC constrained by XRD, EXAFS, and ab-initio results. The fcc-Al nanocrystals nucleated and grown in thin-film specimens have a limited size with almost perfect spherical morphology. The population of these nanocrystals is three orders of magnitude higher as compared to ribbon specimens. The differences in the devitrified ribbon and thin-film metallic glasses were traced back to structural differences in the amorphous state. The amorphous melt-spun ribbons and magnetron sputtered thin- films were found to have different degrees of short-range order and clustering.