A nickel-mediated tandem double cyclization of ethynylene-linked dibromodiporphyrins afforded highly reactive etheno-fused diporphyrins, which undergo a thermal [2+2] cycloaddition at the fused C-C double bond to afford the cyclobutane moiety in X-shaped cyclobutane-linked tetraporphyrins. During the reaction of a Zn(II) complex precursor, the initial double cyclization product was converted into the diketodiporphyrin, which exhibits red chemiluminescence under ambient conditions.