Homopolymerization of N-pyrimidinyl acrylamide (NPA) was reported for the first time. The polymer (polyNPA) was soluble only in acidic media and fluoroalcohols, and only in fluoroalcohol was homogeneous polymerization of NPA feasible. 1 H NMR analysis proved that a 1:1 H-bonding complex could be formed between NPA and α,α-bis(trifluoromethyl)phenyl propan-2-ol (BTMP). Cumyl dithiobenzoate mediated reversible addition-fragmentation chain transfer (RAFT) polymerization of NPA in BTMP was carried out. 1 H NMR analyses proved that the molecular weight increased linearly with the monomer conversion. The polymer prepared in conventional solvents was atactic while in protic media the syndiotacticity was slightly enhanced.