The aim of this work was to synthesize a novel hydrophilic structure based on polystyrene (PS) cross-linked by using N,N '-(hexane-1,6-diyl)diacrylamide (HDBPA). FT-IR was carried out for chemical structure characterization of HDBPA and cross-linked samples. In addition to FT-IR,H-1 NMR was also applied on HDBPA for more investigations. The results showed that HDBPA was synthetized through a condensation reaction, and consequently, it could successfully cross-link PS structure. Moreover, the determination of nitrogen content in HDBPA within PS network was investigated by means of elemental analysis. Afterward, the reactivity ratios between HDBPA and styrene were calculated via Fineman-Ross equation in which the obtained values were 0.66 and 0.23, respectively. On the other hand, by adding the HDBPA to PS the water contact angle was decreased from 73.6 degrees to 57.4 degrees, thereby proving the indispensable role of the cross-linking agent on hydrophilicity of the samples. Finally, the thermal behavior of the samples was studied using DSC and TGA analyses. According to DSC thermograms, there was a shift inT(g)up to 30 degrees C for the samples with cross-linking densities ranging from 2.5 to 20 mol.%. In regard to the thermal stability of the cross-linked samples, the TGA curves revealed a reduction in this property owing to the presence of amide groups in HDBPA through the PS structure.