After irradiation the solution of 1:1 2C-WP5Atrans-G with UV light at 365 nm for 10 min, some new signals appeared as shown in Fig. 2c. In comparison to the signals of individual G at the same experimental condition (Fig. 2d), we observed that the chemical shift of proton Hi* shifted upfield from 3.75 ppm to 1.71 ppm, and the peaks of the protons related to the azobenzene altered slightly (he*, hf*, hg* and hh* Δδ = 0.15, 0.06, −0.13 and −0.92 ppm, respectively). Those changes indicated that the ring B was deshielded by aromatic ring of pillararene, and the methyl group was more shielded than others, which implied the most of azobenzene unit was threaded out of pillararene for 2C-WP5Acis-G. The complexion of 2C-WP5AG exhibited photo-responsive and thermal-responsive as well, the reversible switchable process of the inclusion complex between 2C-WP5A and G could be modulated upon irradiation with UV at 365 nm and heating at 80 °C for one hour (Fig. 2e).