Light-responsive supramolecular interfaces rely on controlling molecular motion within confined environments. We investigated how geometric restriction inside cyclodextrin hosts influences the photoactivity of azobenzene at solid interfaces. Host–guest assemblies were formed between surface-bound azobenzene and α-, β-, or γ-cyclodextrin, and their behavior under illumination was examined using force measurements combined with spectroscopic verification of complex formation. Smaller cavities markedly limited structural rearrangement of azobenzene, while the more spacious γ-cyclodextrin environment preserved substantial photoisomerization. The results indicate that available free volume within the host directly regulates photochemical mobility, providing practical guidelines for engineering mechanically stable yet optically responsive molecular systems