Poly(tetrahydropyrimidine)s are promising heterocyclic polymers with unique biocompatibility, antibacterial ability, inherent fluorescence property, and so on, whose development is limited by their synthetic approaches. Multicomponent polymerizations (MCPs) are a group of powerful tools for the facile construction of heterocyclic polymers from simple monomers. Herein, a catalyst-free multicomponent tandem polymerization of aliphatic diamines, activated alkyne, and formaldehyde was developed at 60 °C in methanol in air to construct poly(tetrahydropyrimidine)s with well-defined structures, high molecular weights (M w up to 57700 g mol −1 ), high yields (up to 84%), and satisfactory thermal stability. The MCP was featured with commercially available monomers, high efficiency, catalyst-free economic and mild condition, which was applicable to aliphatic diamines with complicated chemical reactivity, providing a robust and efficient approach for the synthesis of diversified heterocyclic polymers such as poly(tetrahydropyrimidine)s.