The switching of molecular recognition selectivity is important for tuning molecular functions based on host–guest binding. While the switching processes in artificial functional molecules are usually driven by changes of the thermodynamic stabilities, non-equilibrium phenomena also play an important role in biological systems. Thus, here we designed a host–guest system utilizing a non-equilibrium kinetically trapped state for on-demand and time-programmable control of molecular functions. We synthesized a bis(saloph) macrocyclic cobalt(III) metallohost 1(OTf)2, which has anion caps at both sides of the cation-binding site. The anion caps effectively retard the guest uptake/release so that we can easily make a non-equilibrium kinetically trapped state. Indeed, we can obtain a long-lived kinetically trapped state {[1·K]3++La3+} prior to the formation of the thermodynamically more stable state {[1·La]5++K+}. The guest exchange to the more stable state from this kinetically trapped state is significantly accelerated by exchange of TfO− anion caps by AcO− in an on-demand manner.