Copolymers of methyl methacrylate (MMA), and the methacrylic monomers derived from salicylic acid, 2-hydroxy-4-methacrylamidobenzoic acid (4-HMA), and 2-hydroxy-5-methacrylamidobenzoic acid (5-HMA), were prepared by free radical polymerization in N, N-dimethylformamide, DMF, solution at 50°C using 2, 2′-azobisisobutyronitrile (AIBN), as initiator. Fineman–Ross and Kelen–Tüdos linearization methods, as well as the Tidwell and Mortimer non-linear least-squares treatment were used to calculate the monomers reactivity ratios, giving the Tidwell and Mortimer values from the 95% confidence diagrams, the most probable ones r4=0.83, rM=1.52 and r5=0.29 rM=2.15. The microstructural analysis of the prepared copolymers was performed by 13C (75.5MHz) nuclear magnetic resonance (NMR) spectroscopy, in terms of sequence distribution and stereochemistry of monomeric units along the copolymer chains. The stereochemical parameters σ*=σ4M=σM4=0.21 and σ*=σ5M=σM5=0.19 were determined from the 13C NMR spectra of the copolymers 4-HMA–MMA and 5-HMA–MMA, respectively. Also the Tg of the corresponding homopolymers and copolymers, were analysed by differential scanning calorimetry (DSC) in terms of the Fox equation. Hydration degree of the prepared copolymers was studied in comparison to poly (4-HMA), poly (5-HMA) and poly (MMA).