Anthracene-based cylindrical macrotricyclic polyether (1) containing two dibenzo-30-crown-10 cavities has been proved to be an efficient host for the templated complexation with N,N′-dipropyl-1,4,5,8-naphthalenetetracarboxylic diimide in the presence of lithium ions in both solution and solid state. Host 1 could also form 1:1 complex with the bispyridinium salt with two β-hydroxyethyl groups in solution and in the solid state. Moreover, it was also found that the switchable complexation processes between the macrotricyclic host and two different kinds of guests could be chemically controlled by the addition and removal of lithium ions.