Sub-diffraction-limit imaging can be achieved by sequential localization of photoactivatable fluorophores, where the image resolution depends on the number of photons detected per localization. Here, we report a strategy for fluorophore caging that creates photoactivatable probes with high photon yields. Upon photoactivation, these probes can provide 104–106 photons per localization and allow imaging of fixed samples with resolutions of several nanometers. This strategy can be applied to many fluorophores across the visible spectrum