Using stepwise coupling polymerization method, three ladder-like poly(allylsilsesquioxane)s have been synthesized. The prepared ladder-like polymers contain (i) allyl, (ii) allyl and methyl and (iii) allyl and phenyl as side chain groups. They were characterized by FTIR, NMR, WAXD, DSC and TGA. Characterization indicated that they had ladder-like structure. All the polymers were cured by 2,2'-dibenzoyl peroxide (1% W/W) and the kinetics for the bulk polymerization of these polysilsesquioxanes was followed by dynamic DSC. The Ozawa and Kissinger methods were used to calculate activation energies for curing of these polysilisesquioxanes. Cured samples were characterized by FTIR, DSC and TGA.