A branched polymeric ionic liquid (PIL) with imidazolium cation segments in the main chain connecting branching points was prepared in 95% yield by heating an equimolar mixture of 1,3,5-tris-(4-chlorobutoxy)-benzene and 1,3,5-tris- (4-imidazol-1-yl-butoxy)-benzene at 80 °C for 16 h. Similarly, condensation of a mixture of 1,3,5-tris-(4-imidazol-1-yl-butoxy)-benzene and 1,4-dichlorobutane in 1:1.5 molar ratio produced a second branched PIL in 94% yield. These branched PILs were characterized by FT-IR, 1H, 13C NMR, TGA, and elemental analysis. © Springer-Verlag 2011.