Thin films of Y2O3 are deposited on Si(100) and Al2O3 (0001) substrates via metal‐organic (MO)CVD for the first time using two closely related yttrium tris‐amidinate compounds as precursors in the presence of oxygen in the temperature range 400–700 °C. The structural, morphological, and compositional features of the films are investigated in detail. At deposition temperatures of 500 °C and higher both the precursors yield polycrystalline Y2O3 thin films in the cubic phase. The compositional analysis revealed the formation of nearly stoichiometric Y2O3. The optical band gaps are estimated using UV‐Vis spectroscopy. Preliminary electrical measurements are performed in the form of a metal oxide semiconductor (MOS) structure of Al/Y2O3/p‐Si/Ag. Leakage currents and dielectric constants are also determined.