A styrene-divinylbenzene copolymer functionalized with aldehyde was prepared under phase transfer catalyzed (PTC) conditions. A statistical method for the calculation of the degree of functionalization with aldehyde groups is proposed. The degree of functionalization with aldehyde groups is relatively high. Styrene-divinylbenzene polymers functionalized with benzaldehyde groups were used in Wittig-Horner reaction, in order to introduce double bonds on polymers. The reactions were carried out using PTC method, solid-liquid-solid (s-l-s) (K2CO3, tetrahydrofuran, tetraethylammonium iodide) system. Phase transfer catalyzed reactions are often more easily and cheaply carried out than conventional method and they are therefore of particular interest.