Ordered reactive ladderlike polyallylsilsesquioxane (hereafter referred to as Allyl-T) and polyvinylsilsesquioxane (hereaftef VI-T) were synthesized via stepwise coupling polymerization. During this reaction, coupling agent p-phenyl enediamine (PDA) is supposed to act as a template which enables silane molecules to self-assemble through strong hydrogen-bonding interaction between SI-OH groups and N-H groups. The structure of the polymers was characterized by IR, X-ray diffraction, DSC, GPC, H-1-NMR, C-13-NMR and Si-29-NMR. The data show that the two polymers have ordered ladderlike molecular structure. Hence, the stepwise coupling polymerization is suitable to synthesize ladderlike polysilsesquioxanes (LPSs) containing grafted reactive vinyl-terminated groups.