A comprehensive study of the structural, spectral and energetic properties of chloroboron(III) complexes of subphthalocyanine (H[Formula: see text]SubPc, for the first time) and dodecafluorosubphthalocyanine (F[Formula: see text]SubPc, reinvestigation) was performed by mass-spectroscopy (MS), gas-phase electron diffraction (GED), IR spectroscopy and quantum-chemical (QC) calculations. A synchronous GED/MS method showed that at T = 630 K and T = 540 K, thermally stable H[Formula: see text]SubPc and F[Formula: see text]SubPc molecular forms are present in the gas phase. The geometric structure of free molecules has been determined, in which the N3-B-Cl fragment has the structure of a distorted tetrahedron, and the phthalocyanine skeleton has a dome shape. QC calculations of the geometry agree well with the GED results. The similarities and differences of the molecular structure in the gas and solid phases were discussed. It is shown, that despite the similarity of most geometric parameters, the H[Formula: see text]SubPc and F[Formula: see text]SubPc have significant differences in electronic characteristics, which determines the differences in their physicochemical properties. The interpretation of the experimental IR spectra was carried out. The distribution of potential energy of normal vibrations over the internal vibrational coordinates has been analyzed. The sublimation enthalpies of H[Formula: see text]SubPc ([Formula: see text]H[Formula: see text](589 K) = 135(5) kJ ⋅ mol[Formula: see text] and F[Formula: see text]SubPc ([Formula: see text]H[Formula: see text](516 K) = 189(3) kJ ⋅ mol[Formula: see text] were determined by the mass spectrometric Knudsen effusion method. The obtained data is important for designing processes employed in fabricating optoelectronic devices based on subphthalocyanines by PVD. Experimental geometric parameters for free molecules and vibrational frequencies can be used to calculate the thermodynamic functions of gaseous H[Formula: see text]SubPc and F[Formula: see text]SubPc.