A new synthetic way for obtaining poly(vinyl alcohol) functionalized with maleimide by the acetalization of poly(vinyl alcohol) with 4-formylphenyl-4-maleimidobenzoate and its cycloadducts with furan or anthracene to give the corresponding acetal was studied in detail. The deprotection of modified poly(vinyl alcohol) leaves the double bond of maleimide available for subsequent photocrosslinking, "thiol click" or Diels-Alder reactions. The synthesized structures were confirmed by the Fourier transform infrared and the nuclear magnetic resonance (NMR) spectroscopy. The thermal deprotection of modified poly(vinyl alcohol) was investigated by the means of differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), NMR spectroscopy and TG-DSC/FTIR/mass spectrometer system.