Nanosized spinelCoAl2-xRexO4complex oxides were prepared by self-propagation combustion method. The products have been characterized by XRD, SEM, and EDS. The results indicated that Al3+can be partly replaced by Re3+when the doped amount is less than 10%, which forms single solid solution. The NIR reflectance and chromatic properties of samples have also been investigated. The substitution of Re3+for Al3+in CoAl2O4can increase the blueness of pigments. SEM results revealed that the obtainedCoAl2-xRexO4pigments consisted of highly dispersed spherical-like nanoparticles with uniform size distribution. EDS results indicated that the distribution of element was considerably uniform with no chemical segregation phenomenon.