AbstractWe have synthesised and characterised three sets of acryloyl(amino‐acid)/NIPAAm co‐polymers. Three different co‐monomers were synthesised and copolymerized with N‐isopropylacrylamide (NIPAAm) by free radical polymerization in different molar ratios (12:1, 9:1, and 6:1). All series contain aliphatic spacers and are carboxylic terminated. The effect of co‐monomer nature and content on the glass transition and the LCST transition in solution has been investigated. The main factor affecting the glass transition and the LCST of the polymer was found to be the side chain length of the co‐monomer. The introduction of the co‐monomer resulted in an overall increase in the polymer hydrophobicity which led to a decrease of both the polymer glass transition and the LCST transition observed in solution.