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Global intramolecular hydrogen bonds were installed and manipulated in a rigid artificial synthetic polymer in order to actively control its conformation for synthesis and processing. The polymer solubility was switched on and off by chemically inhibiting and regenerating these preorganized intramolecular hydrogen bonds. Such active manipulation made it possible to synthesize this highly rigid polymer with elevated molecular weights. A well-solubilized, noncoplanar polymer precursor with thermally cleavable Boc groups was synthesized (Mn = 32.4 kg/mol). After processing this precursor into thin films, in situ thermal treatment regenerated the latent intramolecular hydrogen bonds and led to a rigid ladder-type conformation. Such manipulation of the intramolecular hydrogen bonds allowed for multilayer deposition of this polymer, laying the foundation for potential additive manufacturing using this strategy.