This paper presents a compressive study on the fabrication and optimization of GaAs metal–oxide–semiconductor (MOS) structures comprising a Al2O3 gate oxide, deposited via atomic layer deposition (ALD), with an AlN interfacial passivation layer prepared in situ via metal–organic chemical vapor deposition (MOCVD). The established protocol afforded self-limiting growth of Al2O3 in the atmospheric MOCVD reactor. Consequently, this enabled successive growth of MOCVD-formed AlN and ALD-formed Al2O3 layers on the GaAs substrate. The effects of AlN thickness, post-deposition anneal (PDA) conditions, and crystal orientation of the GaAs substrate on the electrical properties of the resulting MOS capacitors were investigated. Thin AlN passivation layers afforded incorporation of optimum amounts of nitrogen, leading to good capacitance–voltage (C–V) characteristics with reduced frequency dispersion. In contrast, excessively thick AlN passivation layers degraded the interface, thereby increasing the interfacial density of states (Dit) near the midgap and reducing the conduction band offset. To further improve the interface with the thin AlN passivation layers, the PDA conditions were optimized. Using wet nitrogen at 600 °C was effective to reduce Dit to below 2 × 1012 cm−2 eV−1. Using a (111)A substrate was also effective in reducing the frequency dispersion of accumulation capacitance, thus suggesting the suppression of traps in GaAs located near the dielectric/GaAs interface. The current findings suggest that using an atmosphere ALD process with in situ AlN passivation using the current MOCVD system could be an efficient solution to improving GaAs MOS interfaces.