Abstract: The red shift of the absorption spectrum of CO.sub.2 with increasing temperature permits the use of sunlight to photolyze CO.sub.2 to CO. The process of the present invention includes: preheating CO.sub.2 to near 1800 K; exposing the preheated CO.sub.2 to sunlight, whereby CO, O.sub.2 and O are produced; and cooling the hot product mix by rapid admixture with room temperature CO.sub.2. The excess thermal energy may be used to produce electricity and to heat additional CO.sub.2 for subsequent process steps. The product CO may be used to generate H.sub.2 by the shift reaction or to synthesize methanol.