This work documents the first example of deposition of high-quality Gd2O3 thin films in a surface-controlled, self-limiting manner by a water-based atomic layer deposition (ALD) process using the engineered homoleptic gadolinium guanidinate precursor [Gd(DPDMG)(3)]. The potential of this class of compound is demonstrated in terms of a true ALD process, exhibiting pronounced growth rates, a high-quality interface between the film and the Substrate without the need for any additional surface treatment prior to the film deposition, and most importantly, encouraging electrical properties.