From the reported experience, primary nanocrystallization in amorphous Al alloys involves transient kinetic behavior that is sensitive to the initial as-quenched structural arrangements. In order to examine the precursor effects, systematic studies outlining the evolving growth kinetics of primary aluminum nanocrystals (nc) during pre-crystallization annealing treatments, and investigations on the microstructure refining effect of specific alloying substitutions represent new approaches for an analysis of primary phase crystallization kinetics. In Al88Ni8Sm4 melt-spun ribbon (MSR), incremental substitutions of Cu for Ni (0 − 1at%) affect the thermal stability of the material (crystallization onset shifts to lower temperature) and refine the size of the primary phase nanocrystals. However, continuous heating calorimetry measurements indicate that the primary crystallization enthalpy remains approximately constant with increased Cu substitution. From a structural analysis standpoint, quantitative microstructure examinations applied in parallel with calorimetry measurements have been employed to characterize the as-quenched volume of MSR samples. The increased primary Al nanocrystal particle density with Cu substitution reflects the modification of local structural arrangements, necessitating an understanding of the local structure of the as-quenched sample in order to develop a description of primary phase nanocrystal growth kinetics.