The anionic polymerization of N-acryloyl-N＇-(4-methylbenzoyl)urea (1) was carried out at 80 degrees C for 24 h in DMF, DMSO, acetonitrile, or toluene by t-BuOK or DBU (3 mol %) as an initiator to obtain polymer 3 in a good yield. The structure of 3 was dependent upon the initiator used, in which t-BuOK selectively conducted the hydrogen-transfer polymerization, while DBU partially induced the vinyl polymerization (16-20%). Likewise, N-acryloyl-N-methyl-N＇-(4-methylbenzoyl) (2, i.e., an N-methylated derivative of 1) was subjected to the hydrogen-transfer polymerization. Although the yield of the polymer was lower in comparison with 1, the structure of the obtained polymer 4 was similarly governed by the initiator.