The new three-dimensional coordination polymer termed {[Na₂SDC(H₂O)]}_n (SDC^2-= C₁₆H₁₀O₄^2-) has been synthesized using workstation Easymax 102 while controlling the conditions and monitoring in-situ reagents. The metal complex was obtained in the reaction of sodium hydroxide with a suspension of 4,4’-stilbenedicarboxylic acid in aqueous medium. The compound was characterized by elemental analysis, single crystal, and powder X-ray diffraction methods, ATR-FTIR spectroscopy, SEM and optical microscopy, TG-DSC and TG-FTIR thermal analysis in air and nitrogen atmosphere. In the crystal structure of {[Na₂SDC(H₂O)]}_n appears penta- and hexacoordinated sodium atoms joined by octa- and decadentate SDC2- linkers. Aqua ligand acts as bridge between Na1 and Na2 atoms. The as-synthesized sodium complex is thermally stable up to 86^oC whereas its dehydrated form has extreme stability up to 491^oC. Removal of water molecule leads to the crystal-to-crystal transformation yielded changes in coordination modes of COO groups. Reversibility of the hydration process in the studied complex was also examined.