A novel supramolecular polymer Q[14]-TBPyP was successfully constructed from a host twisted cucurbit[14] (Q[14]) molecule and a four-arm 5,10,15,20-tetrakis(N-butyl-4-pyridinium)porphyrin tetrabromide (TBPyP) guest molecule depending on the host–guest interactions and characterized by NMR, ITC, DLS, electronic absorption, and fluorescence spectroscopy, representing the first cucurbit[14]uril-involved host–guest supramolecular polymer.