Abstract: Cobalt blue pigment was prepared by self-propagating combustion and calcination from xerogel precursor prepared by sol-gel method. Factors influencing the gel formation and combustion characteristics as well as the crystal structure of prepared cobalt blue were investigated，such as citric acid amount，sol reaction temperature，pH value，concentration of metal ions and ethylene glycol. Effects of thermal treatment methods and calcination temperature of the xerogel on the crystal structure of cobalt blue pigment were also investigated. Results showed that citric acid amount，sol reaction temperature and ethylene glycol have no effects on the crystal structure of cobalt blue pigment. The increasing in sol reaction temperature and concentration of Co2+ and Al3+（0.01～0.1mol /L ）was conducive to rapid gel formation. When the total Co2+ and Al3+concentration was as low as 0.005 mol / L，the cobalt blue pigment could not be formed with intact spinel structure. Suitable pH value（about 6.5）was favorable to citric acid ionization and complexation with metal ions，as well as the succeeding gel self-propagating combustion. Glycol could improve the agglomeration of cobalt blue pigment. Cobalt blue pigment with intact spinel structure could also not be formed just by gel self-propagating combustion. The crystal structure and dispersion properties of cobalt blue pigment could be improved by the combination of self-propagating combustion and calcination. By calcination after self-propagating combustion，cobalt blue pigment was obtained with more complete crystal structure and with brighter colors with the increasing of calcination temperature.