A new type of solid-state crystalline photopolymerization is researched in which, different from the topochemical polymerization, vinyl monomers are filmed under the induction of other macromolecular compound, crystallized, and polymerized after photoirradiation. Therefore, it may be also known as induction-filming polymerization. The crystalline polyacrylamide film with large spherulite structures was obtained from the crystalline acrylamide by this means. Microscopy, differential scanning colorimetry, and infrared measurements were carried out. Mechanism is proposed for the induction-filming polymerization involved.