A novel supramolecular complex formed by N,N'-diethyl viologen (EV2+) and symmetrical tetramethylcucurbit[6]uril (TMeQ[6]) was described both in solution and in the solid state by H-1 NMR, UV spectroscopy and Single-crystal structure analysis. In the solid state, EV2+ and TMeQ[6] formed two types of inclusion models in the self-assembled complex, a pseudorotaxane of a N,N'-diethyl viologen threading into the cavity of TMeQ[6] and a dumbbell-like structure of a N, N'-diethyl viologen shouldering two TMeQ[6] molecules, and the two types of complexes assembled to 1D supramolecular chain through hydrogen bonding. (C) 2011 Published by Elsevier B.V.