The chemical synthesis conditions (TiCl4: iPrOH reagent ratio and reaction temperature scheme) were optimized for the preparation of polymeric titanium oxychloride sorbent which met the requirements for clinically useful 188W/188Re generator production, such as high W-adsorption capacity, high 188Re-elution yield, low 188W-breakthrough, and good mechanical stability. This polymeric material was formed by polycondensation of titanium-oxychloride units, the chemical formula of which was supposed as [OTiO (Ti40 Cl80 (OH) 80 (TiO2)95.60H2O) OTiO]n. The effect of the W-content of tungstate solution on the WO42- ion adsorption (with minimizing the poly-tungstate ion adsorption) and its covalent bonding with the Ti metal atoms in the polymeric matrix were justified with respect to the optimal W-adsorption conditions for the preparation of a useful 188W/188Re generator column. The high W-adsorption capacity of about 515.6mg W/g sorbent and 188Re elution yield of higher than 85% wereachieved. The large difference in the distribution ratio values found for alumina and polymeric titanium oxychloride sorbent in 0.005% NaCl solution (DW,Re-188=50 and DW, Re-188=1.0, respectively) offered an advantage for the preparation of a consecutive-elution based 188Re generator system which combined both 188Re elution and 188Re concentrating processes in one portable system. This generator system is of a tandem column type which consists of a polymeric titanium oxychloride sorbent coupled to an alumina column. This system gave a 188Re concentration factor of approximately 10. The overall 188Re yield achieved from this system was 80%. 188W isotope and elemental tungsten breakthrough were not detected in its 188Re eluate. This system thus offers a potential application for clinically useful 188Re production using low specific radioactivity 188W (around 500mCi/g) producible in a medium neutron flux reactor.