The color scheme in the photo plays an important role in emotional perception and esthetic assessment of images. In this scientific article the technique of creation of non-standard color schemes is presented to photos and their influence on emotional perception and esthetic assessment of the viewer. Various theories of color perception and psychology of color and also methods of the analysis of color schemes in the photo are considered. The main attention is paid to a communication research between colors and emotional reactions and also to influence of color combinations on esthetic assessment of photos. This technique and a research will help photographers and designers to create the new non-standard, but harmonious and emotionally filled color schemes in the works.