The photochemistry of CO and its isotoplogues affects the structure and evolution of many astronomical environments, including interstellar clouds, circumstellar disks around newly formed stars, and the envelopes surrounding highly evolved stars. When in the presence of a strong ultraviolet field, the primary destruction mechanism for interstellar and circumstellar CO is photodissociation, which is entirely governed by discrete line absorption into predissociating levels in the wavelength range 91.2 to 111.8 nm. Because the CO spectrum consists primarily of resolved line features, self-shielding effects in high-column density environments can lead to strong isotopic fractionation signatures in both CO and elemental oxygen and carbon; for example, CO self-shielding in the solar nebula has been invoked to explain the unusual oxygen isotope ratios observed in the earliest solar system condensates, viz. calcium-aluminum inclusions (CAIs) in primitive meteorites.