Alcohol exchange reactions applied to HfAl 2(OPr i ) 10 ( 1) afforded heterometallic Hf–Al aminoalkoxides namely HfAl 2(OPr i ) 8(dmae) 2 (dmae = N, N-dimethylaminoethoxide) ( 2) and HfAl 2(OPr i ) 8(dmap) 2 (dmap = dimethylaminopropoxide) ( 3). They were characterized by elemental analysis, FT-IR, 1H NMR, mass spectrometry and TGA. The molecular structure of 2, as established by single-crystal X-ray diffraction, HfAl 2(μ-OPr i ) 2(μ,η 2-OC 2H 4NMe 2) 2(OPr i ) 6, is based on an open-shell trinuclear unit with a central 6-coordinate Hf atom and 5-coordinate Al centres. Compound 2 was tested as a single-source precursor for the deposition of hafnium aluminate films by liquid-injection MOCVD. The films growth rate, composition and morphology were studied in relation with the deposition temperature. The as-deposited at 500–800 °C films (both on sapphire and silicon) were amorphous; partial crystallization occurred after 1 h annealing at 900 °C. The bulk of the films was Al-rich (Al/Hf = 1.2–1.6) and contained small amounts of carbon (2–4%) and nitrogen (4–5%).