A novel β-cyclodextrin dimer bearing 2, 9-diformyl-1, 10-phenanthroline tether 4 has been synthesized and its inclusion complexation behavior with two triangular model substrates(RhB and BG) has been investigated through fluorcseence and ultraviolet spectrometry. The result obtained indicated that novel bridged bis(β-cyclodcxtrin)s could significantly enhance the original molecular binding ability of native β-cyclodextrin by coopcrative binding of two hydrophobie cavities.