Water‐soluble copolymers from mono‐1‐alkyl itaconates and N‐vinyl‐2‐pyrrolidone are synthesized and characterized. The mono‐1‐alkyl itaconates are prepared from itaconic anhydride and the related alcohol: 1‐dodecanol, 1‐octadecanol, 1‐docosanol, and 1‐triacontanol. The mono‐1‐triacontyl itaconate is synthesized from plant growth regulator policosanols extracted from Agave fourcrouydes, where 1‐triacontanol is the major product. The reactivity ratios, calculated according to the Mao‐Huglin method for copolymerizations conducted to medium‐high conversions, indicate a tendency toward alternation for all copolymerization reactions. Water solubility of copolymers is provided as a function of copolymer composition and aliphatic chain length. magnified image