By means of particular examples, the present work demonstrates the possibility of directed delicate non-destructive control of structure, composition and properties of inorganic solids using the method of selective chemical vapor transport (SCVT). Gallium monoselenide GaSe is the main model object. Additional, though less detailed, explanation is given by the example of gallium monosulfide GaS. Experimental evidences on the possibility of the control of polytypic structure, non-stoichiometry and properties of gallium monoselenide were obtained in non-isothermal variant of selective chemical vapor transport which has non-destructive character. Diagnostics of the phase (polytypic) composition and non-stoichiometry of GaSe was performed with the use of X-ray diffractometry as well as with the use of cathode luminescence spectra. It was experimentally found that there exists a connection of non-stoichiometry and the properties of gallium selenides with the determining conditions of selective chemical vapor transport: temperature of controlled sample (T-2) and the difference of temperatures between the hot and cold zones (Delta T). It is shown that the phase diagram of Ga-Se system needs to be partially revised near the composition of Ga1Se1. The reason for such revision is the fact that two polytypes (epsilon-GaSe and gamma-GaSe) exist on this phase diagram as independent phases. (C) 2011 Elsevier B.V. All rights reserved.