Poly(vinyl alcohol) (PVA) was esterified with 10-undecenoyl chloride to give polymers with different degrees of modification which were studied in order to find how the concentration of reactive sites can influence the crosslinking process. The polymers obtained were characterized by spectroscopic techniques, elemental analysis and thermal methods. Weight average molecular weights and viscosities were determined. Thermal crosslinking of the double bonds on the side chain took place in all cases, but was overlapped by the degradation process. Thus, dicumyl peroxide had to be used to obtain the cured material and avoid degradation. Activation energies for radical initiated crosslinking were determined by means of dynamic DSC studies. Isoconversional kinetic analysis was applied to DSC data and the dependences of activation energies on conversion degrees were obtained and compared with those obtained from polymers with the same pendant chain but a more flexible polyether main chain.