A 2D polypseudorotaxane-type assembly was constructed using cucurbit[8]uril and styrylpyridinium-bearing triphenylamine. In addition, tunable non-covalent to covalent transition was achieved by [2+2] photodimerization of styrylpyridinium units. Thus, a more stable 2D polyrotaxane-type nanoarchitecture was obtained, which could capture [60]fullerene and further exhibit an excellent photodynamic therapy effect.