Three diamine compounds with an anthracene bridge were synthesized and characterized, including 1,5-bis(di-p-anisylamine)anthracene (1), 2,6-bis(di-p-anisylamine)anthracene (2) and 9,10-bis(di-p-anisylamine)anthracene (3). The electrochemistry, absorption and emission spectra, spectroelectrochemistry, and amine-amine electronic coupling of these compounds were examined. All compounds display two consecutive redox couples in the potential region between +0.6 and + 1.0 V vs Ag/AgCl, with a potential splitting AE of around 100 mV. In the one-electron-oxidized state, weak intervalence charge transfer (IVCT) transitions were observed for 1(center dot+) in the near-infrared (NIR) region and the electronic coupling parameter V-ab was calculated to be 600 cm(-1). In contrast, compound 3(center dot+) displays an intense IVCT band in the NIR region with a V-ab value of 1440 cm(-1). However, no distinct IVCT band was discernable for 2(center dot+), indicative of an eligible electronic coupling. This work demonstrates that the positions of the amine substituents on the anthracene bridge play a critical role in determining the degree of amine-amine electronic coupling.