© 2018 Elsevier B.V.Cross-linking of polyvinyl alcohol (PVA) was achieved by using functional 1,3,5-triazinanes and formaldehyde as cross-linking agents. This method can be considered as an alternative to acetalization of PVA by monoaldehydes. The gels obtained with the triazinane method exhibited dimensional stability and resistance against acids. Control experiments were performed to have a better insight of the gelation process. The products of control experiments and obtained gels were characterized spectroscopically by FTIR and 1H NMR and thermally by DSC. Moreover, swelling in water and acid stability of gels were investigated and compared to the PVA–formaldehyde system.