Effects of catalysts on network structure, hard segment length and distribution of polyurethane foams in the absence of catalysts were investigated. CFC free all MDI-based poly urethane foams were prepared from poly(ethylene adipate)glycol, 4,4'-diphenylmethane diisocyanate, and water. Amino catalysts used were 1,4-diazabicyclo[2,2,2]octane(DABCO), N, N,N',N'-tetramethyl--hexane-1,6-diamine(MR), bis(2-methylamino ethyl)ether(ET), 1,8-diazabicyclo-[5,4,0]-undecene-7(DBU). Dibutyltindilaurate(DBTL) as control was also used. Hard segment components of polyurethane foams were obtained by a selective degradation of polyester chains with 0.01N KOH-methanol solution. The PUFs with DBU catalyst contained more amount of isocyanurate components than other PUFs. On the other hand, the PUFs with ET, MR, DBTL catalysts contained more amount of allophanate and biuret component than the other PUFs.