Pillar[n]arenes, known as the fifth generation of host macrocycles since 2008, have become a popular topic over the past ten years. Until now, the studies of pillar[n]arenes were mainly focused on pillar[5]arenes owing to their easy synthesis and high yields. In particular, 1,4-dimethoxypillar[5]arene (DMP5), which shows a simple structure, efficient synthesis and high yield, has played important roles in the construction of various advanced supramolecular architectures. However, DMP5 has only displayed host-guest binding properties towards some guests. Therefore, the investigation of the host-guest chemistry of DMP5 should be able to greatly promote the development of pillararene chemistry. Herein, a photosensitive azastilbene derivative was chosen as a neutral guest to study the host-guest binding and stimuli-responsive behavior with DMP5. In addition, the binding behavior of DMP5 towards a series of analogous neutral guest molecules was investigated to study the driving forces of the host-guest interaction between DMP5 and the azastilbene guest. Moreover, the [2]pseudorotaxane based on DMP5 and the azastilbene guest was used to construct a polypseudorotaxane via metal coordination.