The potential of pyrimidines to serve as ditopic halogen‐bond acceptors is explored. The halogen‐bonded cocrystals formed from solutions of either 5,5′‐bipyrimidine (C8H6N4) or 1,2‐bis(pyrimidin‐5‐yl)ethyne (C10H6N4) and 2 molar equivalents of 1,3‐diiodotetrafluorobenzene (C6F4I2) have a 1:1 composition. Each pyrimidine moiety acts as a single halogen‐bond acceptor and the bipyrimidines act as ditopic halogen‐bond acceptors. In contrast, the activated pyrimidines 2‐ and 5‐{4‐(dimethylamino)phenylethynyl}pyrimidine (C14H13N3) are ditopic halogen‐bond acceptors, and 1:1 halogen‐bonded cocrystals are formed from 1:1 mixtures of each of the activated pyrimidines and either 1,2‐ or 1,3‐diiodotetrafluorobenzene. A 1:1 cocrystal was also formed between 2‐{4‐(dimethylamino)phenylethynyl}pyrimidine and 1,4‐diiodotetrafluorobenzene, while a 2:1 cocrystal was formed between 5‐{4‐(dimethylamino)phenylethynyl}pyrimidine and 1,4‐diiodotetrafluorobenzene. The role of activated pyrimidines and bipyrimidines as ditopic halogen‐bond acceptors is demonstrated.