We report here the preparation of asymmetrical phthalocyanine dimers 1a-3a, which are endowed with novel charge transfer bands at 1,151-1,154 nm and strong NIR luminescences at 840-860 nm and 1,600-1,650 nm. Through H-bonding interaction, 1a-3a are inclined to self-assemble into hexrod nanotubes at the interface of CHCl₃ and CH₃H. Our results provide further insights into the interaction in molecular dimers, and suggest that 1a-3a have potential application in magnets and supramolecular architectures.