Interest to of metals -diketonates is caused by their unique physical-chemists properties. It defines wide application of metals -diketonates in scientific researches, technics, and technologies, for example in fabrication of metallic and metal-oxides surfaces. Strong biological activity of some -diketonates allows its application in antiviral, antiallergic, antitumoral therapeutics, tranquilizators, insecticide, and herbicides. Transition metals acetylacetanates are interesting in fundamental investigations because of its - and - substitution. Variation of the complex forming metal allows to obtain useful data to elucidate metal — ligand interaction, influence of d-orbitals population and multiplicity on electronic structure. Special interest in investigation of aluminium, chromium, and cobalt acetylacetanates is caused by its addition to oligo- and polyorganylsiloxanes compounds. Materials based on [RSiO1.5]n have strong hydrophobic, color stability, and other special photo-properties. Our study of Cr(Acac)3, and their -substituted Cr(Acac)n(Acac-R)m where R = -SCl, or -S-CH2C(Cl)H-SiMe3 (n+m=3) is part of our investigation of organylsiloxanes with connecting chelates metal complexes. Cr(Acac)3 photoelectron spectrum was obtained in gas-phase with HeI source (21.2 eV). Spectra for others compounds were collected in solid measurments with X-ray MgK source (1253.6 eV). DFT/B3LYP calculations with geometry optimization were carried out for all structures. Chromium acetylacetanate sulphenylchloride is presented on the picture.With to photoelectron spectroscopy measurements and quantumchemical modeling we obtain new data in geometric structure, energy properties of the core and valence levels, electronic density localization, chemical states of atoms, and other electronic and energy properties of studied complexes.