The synthesis of four different monofunctional vinyl cyclopropane (VCP) derivatives and their polymerization behavior is presented. The different VCPs have different capabilities to form hydrogen bonds in their side chain. A preorganization due to these hydrogen bonds should lead to a fast polymerization. Kinetic studies, hydrogen-bond strength, and theoretical calculations were used to correlate the degree of conversion and the amount of preorganization. While VCPs capable of hydrogen bonding did not show a huge difference, a general effect of hydrogen bonds on polymerization behavior could be observed.