Investigation of the thermal behavior of Hf(dpm)4 vapor in vacuum is carried out. An approach for obtaining films of (HfO)x(Al2O3)1-x alloys is developed. The use of a source containing a mixture of two precursors differing from each other in volatility, notably Hf(dpm)4 (dpm = dipivaloylmethanate, 2,2,6,6-tetramethylheptane-3,5-dionate) and Al(acac)3 (acac = pentane-2,4-dionate), allows us to employ the possibilities of combinatorial chemistry, and to obtain and analyze a number of different compositions of alloys. Film characterization is performed using a set of analytical methods. The character of Al and Hf distributions across the film thickness, depending on their content in the source, is investigated. The use of laser null ellipsometry allows us to determine the distribution of the refractive index across the thickness of the (HfO)x(Al2O3)1-x film. A comparison of the ellipsometric data with the X-ray photoelectron spectroscopy (XPS) data shows that the character of the refractive index variation reproduces the variation of the chemical composition across the film thickness. A uniform distribution of the elements across the film thickness is observed in the cases when separated sources are used. The structure of the film depends on the molar fraction of Al2O3 in alloys. For Al ≥ 30 at.-% amorphization of the structure occurs.