Identification and synthesis of intramolecularly donor‐stabilized aluminium(III) complexes, which contain a 3‐(dimethylamino)propyl (DMP) ligand, as novel atomic layer deposition (ALD) precursors has enabled the development of new and promising ALD processes for Al2O3 thin films at low temperatures. Key for this promising outcome is the nature of the ligand combination that leads to heteroleptic Al complexes encompassing optimal volatility, thermal stability and reactivity. The first ever example of the application of this family of Al precursors for ALD is reported here. The process shows typical ALD like growth characteristics yielding homogeneous, smooth and high purity Al2O3 thin films that are comparable to Al2O3 layers grown by well‐established, but highly pyrophoric, trimethylaluminium (TMA)‐based ALD processes. This is a significant development based on the fact that these compounds are non‐pyrophoric in nature and therefore should be considered as an alternative to the industrial TMA‐based Al2O3 ALD process used in many technological fields of application. Easy to handle Al precursors: A new class of 3‐(dimethylamino)propylaluminium(III) complexes were developed as novel atomic layer deposition (ALD) precursors, which were successfully applied for low‐temperature thermal and plasma ALD of Al2O3 thin films. The non‐pyrophoric nature of these compounds, as well as the outstanding process characteristics, render them as a real alternative to the industrially used trimethylaluminium process for Al2O3.