The photoswitching of supramolecular host-guest complexes is the basis of numerous molecularly controlled macroscopic functions, such as sol-gel transition, photopharmacology, the active transport of ions or molecules, light-powered molecular machines, and much more. The most commonly used systems employ photoactive azobenzene guests and synthetic host molecules, which bind as the stable E isomers and dissociate as the Z forms after exposure to UV light. We present a new, extraordinarily efficient cucurbit[7]uril (CB7)/diazocine host/guest complex with inverted stability that self-assembles under UV irradiation and dissociates in the dark. The association constants of the Z and E isomers in water differ by more than 104-fold. We also show that the thermally activated E → Z isomerization is significantly accelerated by CB7, which is a rare case of enzyme-like catalysis by transition state stabilization without product inhibition. In contrast to CB7, cucurbit[8]uril (CB8) binds both isomers with high affinity, showing good selectivity (∼1000-fold) toward the Z isomer. Notably, this isomer preferentially binds CB8 relative to CB7 by a factor greater than 1 × 106. We also use the system to introduce a supramolecular photoacid that builds on the increased basicity of a guest bound to CB7 and on the extremely high affinity of the E isomer, which is utilized to displace the acid from CB7, thereby switching the pH of the solution.