Spatio-temporal release of biologically relevant small molecules provides exquisite control over the activation of receptors and signaling pathways. This can be accomplished via a photochemical reaction that releases the desired small molecule in response to irradiation of light. A series of small molecules (serotonin, capsaicin, VNA, octopamine, tyrosine, dopamine, epinephrine, and norepinephrine) that contain either a phenol or catechol moiety were caged using either BHQ or CyHQ. In all cases the CyHQ caged compounds proved sensitive toward 1PE and 2PE processes with quantum efficiencies of 0.2 0.4 upon irradiation at 365 nm and two photon cross sections of 0.15 0.31 GM when irradiated at 740 nm. All but two compounds, BHQ-dopamine and BHQ-estradiol were found to be sensitive to both 1PE and 2PE with quantum efficiencies of 0.30 0.40 and two photon cross sections of 0.40 0.60 GM. CyHQ-epinephrine and CyHQ-norepinephrine possessed a novel photodegradation pathway that was analyzed through radical trapping experiments and product studies