Two kinds of chemical functional single-wall carbon nanotubes (SWNTs) are covalently coupled into special V-type superstructure by the esterification in pyridine medium. Both SWNTs bundles and individual SWNTs can be bound effectively through the deacidification path. The esterification between different kinds of modified SWNTs takes place on their ends and the crystallinity of SWNTs are well remained during the course. Interestingly, the inclinations between coupled SWNTs are very closely to the ester bond angle (109o18’). Furthermore, the formation mechanism about the peculiar structure has been proposed in the paper. The results suggest that selected connection bonds will determine the different angles of coupled SWNTs.