Meldrum's acid (MA) is utilized as a monomer to polymerize with diisocyanates to result in polyamides, containing MA moieties at polymer chains. This reaction is also employed to prepare isocyanate-terminated polyamide segments which are utilized as a precursor for preparation of MA-containing polyurethanes. Based on the thermolysis reaction of MA groups, followed by ketene dimerization reaction, the reactive polyamides and polyurethanes show self-cross-linkable features. The cross-linked polyurethanes exhibit good film formability, thermal stability, and mechanical properties. A new MA-based polymerization method and a novel synthesis route for preparation of reactive polyamides and polyurethanes are demonstrated.