AbstractVinyl‐type monomers containing the pyrrole ring, such as 2‐vinylpyrrole (2‐VPyrr),N‐(pyrrol‐2‐yl)methylacrylamide (PMA),N‐methyl,N‐(pyrrol‐2‐yl)methylacrylamide (MPMA), 2‐allylpyrrole (2‐AP), β‐(pyrrol‐1‐yl)ethyl vinyl ether (PEVE), 2‐diallyl‐aminomethylpyrrole (DAMP), and 3‐(2‐pyrrolylmethyleneimino)propene‐1 (PIP) were synthesized by various reactions involving characteristic properties of the pyrrole ring. Radical homopolymerizations and copolymerizations of these monomers were studied. In the homopolymerization of conjugated monomers such as 2‐VPyrr and PMA, chain transfer to the pyrrole‐containing monomer was remarkable but not degradative. The copolymerization parameters, that is, the values ofr1,r2,Q1, ande1of 2‐VPyrr, were determined to be 0.066, 0.69, 5.53, and −1.36, respectively in the copolymerization of 2‐VPyrr (M1) with MMA (M2). TheQandevalues of the monomers containing a heteroaromatic ring such as 2‐vinylpyrrole, 2‐vinylfuran, and 2‐vinylthiophene were evaluated by the molecular orbital theory. Theevalue of PMA was found to be negative (−0.64) in the copolymerization with styrene, althoughefor acrylamide derivatives is generally positive. This may be explained by the intermolecular hydrogen bonding between the carbonyl group and NH group of PMA. That is, attraction or polarization of π‐electrons in the vinyl group of PMA is weakened by such hydrogen bonding. From the results of copolymerization of 2‐AP with various comonomers, the comonomers could be classified into three categories: class a monomers, in which bothQandevalues are largely positive, can copolymerize with 2‐AP; class b monomers, having smallevalues, homopolymerize and can not copolymerize with 2‐AP; classcmonomers, in which bothQandevalues are small. TheQandevalues of the comonomer must be largely posi