A novel organic-inorganic hybrid-type ladder-like poly(benzylazide) silsesquioxane (LPBAzSQ) and ladder-like poly(propylazide) silsesquioxane (LPPAzSQ) were synthesized through azidation of ladder-like poly(p-chloromethyl) phenylsilsesquioxane (LPCMPSQ) and ladder-like poly(propylchloro) silsesquioxane (LPPCSQ). The ladderlike structure of the synthesized LPBAzSQ and LPPAzSQ compounds, full substitution of azide groups, and their click chemistry with various functional groups was characterized by H-1 NMR, C-13 NMR, Si-29 NMR, FT-IR, GPC. This new approach for functionalization of ladder-like silsesquioxanes has allowed for insertion of polar functional groups that have yet be examined in silsesquioxane chemistry.