Recently,m etastable-state photoacids have been widely used to control protontransfer in numerousc hemical and biologicalp rocesses as well as applicationsw ith visible light. Generally,s ubstituents have ag reat influence on the photochemical properties of molecules, which will further affect their applications. Yet, the effects of substituents on metastable-state photoacids have not been studied systematically.I nt his work, 16 metastable-state photoacid derivatives were designeda nd synthesized on the basis of sub-stituents having al arge range of s-p electron-donor-acceptor capabilities. The effects of substituents on the color display [or maximuma bsorption band(s)], solubility,p K a values,d ark/photoacidity,p hotosensitivity,a nd relaxation kinetic(s) were investigated in detail.T his study will be helpful for the targeted design and synthesis of promisingp hotoacids and the application of their photocontrolled proton-release processes in functional materials/devices.Supporting Information and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.