Aluminum nitride (AlN) film possesses wide band gap energy (~6.2 eV) and a high dielectric constant (~9.2), and is resilient to thermal and chemical stimuli. It also exhibits several functionalities, such as piezoelectricity and pyroelectricity. Therefore, AlN film has been used for electronic and optoelectronic devices and micro-electromechanical systems (MEMSs). Among the various methods of AlN thin film growth, atomic layer deposition (ALD) can control film thickness at the nanoscale. Uniform and conformal film growth is possible at temperatures lower than that of chemical vapor deposition or molecular beam epitaxy. Because the ALD process relies on surface chemical reactions, it shows substrate dependency. To control film uniformity from the beginning, an understanding of nucleation and growth behavior on the substrate is necessary. Therefore, the nature of nucleation and growth behaviors on different substrates is investigated. In this study, AlN films are grown on bare Si and TiN substrates at 295–342 °C by thermal ALD using trimethyl aluminum (TMA) and ammonia. Facile nucleation and linear growth on the TiN substrate, and substrate-inhibited nucleation on the Si substrate, are observed. NH3 pretreatment may enhance the growth rate at the nucleation stage. Therefore, the dissociation of NH3 on the substrate is crucial to making uniform nuclei for the subsequent growth of AlN film.