Hydrothermal reactions of CdCl2, oxalic acid, 1,3,5benzenetricarboxylic acid and ophenylene diamine oPD yielded three novel coordination polymers [NaCd4btc3H2bbim4H2O2]·2H2O 1, [KCd4btc3H2bbim4H2O2]·2H2O 2 and [CdH2bbimH2bimbdcHbimbdcH]·H2O 3 [btc = 1,3,5benzene tricarboxylate, H2bbim = 2,2′bisbenzimidazole, HbimbdcH2= 12Benzimidazolyl3,5benzene dicarboxylic acid]. The benzimidazole derivatives were in situ generated via hydrothermal metalligand condensation of oxalic acid or 1,3,5benzenetricarboxylic acid with ophenylenediamine. Both 1and 2have novel singlewalled nanotubular coordination structures and show strong red photoluminescence at room temperature.© WileyVCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009