The focus of this work is placed on the analysis of the mixture formation process under the evaporative diesel-free spray conditions. In order to examine homogeneity of mixture within the vapor phase region of the injected spray, image analysis was carried out based on the entropy of statistical thermodynamics. As an experimental parameter, the injection pressure and ambient gas density were selected, and effects of the injection pressure and density variation of ambient gas on the mixture formation process in the evaporative diesel spray were investigated. In the case of application of the thermodynamic entropy analysis to evaporative diesel spray, the value of the dimensionless entropy always increases with increase in time from injection start. Consequently, the dimensionless entropy in the case of the higher injection pressure is higher than that of lower injection pressure during initial injection period.