A way to obtain highly ordered and thermally stable crystalline In–Ga–O (IGO) thin films is reported by atomic layer deposition with novel bulky dimethyl[N‐(tert‐butyl)−2‐methoxy‐2‐methylpropan‐1‐amine] gallium precursor. The optimal cation composition for IGO (In:Ga = 4:1 at%) shows a pronounced alignment along the high c‐axis with cubic (222) orientation at a relatively low annealing temperature of 400 °C. Moreover, the crystallinity and oxygen‐related defects persist even at elevated annealing temperatures of 700 °C. Owing to its well‐aligned crystallinity, the optimal IGO thin film transistor demonstrates extremely high field‐effect mobility (µFE) and remarkable thermal stability at high temperatures of 700 °C (µFE: 96.0 → 128.2 cm2 V−1s−1). Also, process‐wise, its excellent step coverage (side: 96%, bottom: 100%), compositional uniformity in a 40:1 aspect ratio structure, superior crystal growth in vertical structures, and excellent reproducibility make it a promising candidate for application as a channel in next‐generation 3D memory devices.