This chapter focuses on the various production routes to manufacture soluble and crosslinked versions of polyvinyl caprolactam (PVCL) by free‐radical polymerization, and how each route can affect the polymer's final properties. It discusses that the methodologies include solution polymerization, emulsion polymerization, and dispersion polymerization routes. N‐VCL is a seven‐membered cyclic amide that is a structural relative to N‐vinyl pyrrolidone. Homopolymerization of N‐VCL using t‐butyl peroxide was only initiated at 100 °C to achieve a decent polymerization level. Several studies have investigated the effect of chain‐transfer agents's on the polymerization kinetics of a N‐VCL polymerization. The chapter shows that many factors influence the free‐radical polymerization rate; from solvent, temperature, initiator‐type, monomer reactivity, additives, and polymerization‐type such as solution, emulsion, or precipitation. PVCL forms clear films with a semigloss appearance that exhibits both hydrophilic and hydrophobic properties. Synthetic approaches have included solution polymerization employing conventional free‐radical polymerization; bulk polymerization, emulsion, precipitation, or suspension polymerization.