Four hybrid 3,3'-(alkane-1,n-di-yl)-bis(1-methyl-1H-imidazole-3-ium) halobismuthates were prepared by a facile solution route and characterized by diffuse reflectance spectra and photoluminescence measurements. Crystal structure of 3,3'-(buthane-1,4-di-yl)-bis(1-methyl-1H-imidazole-3-ium) bromobismuthate (1) contains zero-dimensional Bi2Br10 anions. Crystal structure of 3,3'-(pentane-1,5-di-yl)-bis(1-methyl-1H-imidazole-3-ium) iodobismuthate (4) contains zero-dimensional Bi2I9 anions.