Smart surfaces that can change their wettability on demand are interesting for applications such as self-cleaning surfaces or lab-on-a-chip devices. We have synthesized arylazopyrazole (AAP) phosphonic acids as a new class of photoswitchable molecules for functionalization of aluminum oxide surfaces. AAP monolayers were deposited on α-Al2O3(0001) and showed reversible E/Z photoswitching that can trigger contact angle changes of up to ∼10°. We monitored these changes on the macroscopic level by recording the contact angle while the monolayer was switched in situ. On the molecular level, time-dependent vibrational sum-frequency generation (SFG) spectroscopy provided information on the kinetic changes within the AAP monolayer and the characteristic times for E/Z switching. In addition, vibrational SFG at different relative humidity indicates that the thermal stability of the Z configuration is largely influenced by the presence of water which can stabilize the Z state and hinder E → Z switching of the AAP monolayer when it is wetted with H2O. Having established the switching times on the molecular scale, we additionally measured the dynamic contact angle and show that the time scales of the substrate and droplet dynamics can be extracted individually. For that, we report on a relaxation model that is solved analytically and is verified via a comparison with simulations of a Lennard-Jones system and with experimental data. The slower E to Z switching in the presence of the droplet as compared to the vapor phase is rationalized in terms of specific interactions of water with the exposed AAP moieties.