The reactions of thioaminyl mono- (MONOR) and diradicals (DIR) with 7,7,8,8-tetracyanoquinodimethane (TCNQ) have been investigated. The reactions of TCNQ with MONOR gave 1:2 adducts of TCNQ and MONOR in 85–88% yields, while the reaction with DIR afforded either a cyclophane compound (77%), or an alternating polymer of TCNQ and DIR (59 wt%), dependent on the structures of DIR.