The algorithm of combining a real image with a virtual model was proposed to increase the reality of synthesized images. Currently, synthesizing a real image with a virtual model facilitated the surface reflection model and various geometric techniques. In the current methods, the characteristics of various illuminants in the real image are not sufficiently considered. In addition, despite the chromatic adaptation plays a vital role for accommodating different illuminants in the two media viewing conditions, it is not taken into account in the existing methods. Thus, it is hardly to get high-quality synthesized images. In this paper, we proposed the two-phase image synthesis algorithm. First, the surface reflectance of the maximum high-light region (MHR) was estimated using the three eigenvectors obtained from the principal component analysis (PCA) applied to the surface reflectances of 1269 Munsell samples. The combined spectral value, i.e., the product of surface reflectance and the spectral power distributions (SPDs) of an illuminant, of MHR was then estimated using the three eigenvectors obtained from PCA applied to the products of surface reflectances of Munsell 1269 samples and the SPDs of four CIE Standard Illuminants (A, C, D50, D65). By dividing the average combined spectral values of MHR by the average surface reflectances of MHR, we could estimate the illuminant of a real image. Second, the mixed chromatic adaptation (S-LMS) using an estimated and an external illuminants was applied to the virtual-model image. For evaluating the proposed algorithm, experiments with synthetic and real scenes were performed. It was shown that the proposed method was effective in synthesizing the real and the virtual scenes under various illuminants.