This paper describes a previously unreported class of sterically crowded tetracene derivatives that have both phenyl and ethynyl substituents. The steric crowding above and below the tetracene core prevents overlap between the extended π-systems of the acenes. Substituent effects cause these tetra-substituted tetracenes to have absorbance and fluorescence spectra red shifted from either disubstituted derivatives or rubrenes, such that they have spectra similar to diarylpentacenes, but with higher quantum yields of fluorescence and greater photostability. These new molecules also undergo cycloaddition reactions with ¹O₂, giving regioisomeric mixtures of endoperoxides, and in contrast to longer acenes, the ethynyl substituents show only a modest stabilizing effect to photooxidation. Ethynylated tetracenes also exhibited photochromism, with their endoperoxides undergoing cycloreversion to yield the acene starting material at room temperature in the dark.