Photosensitive polyimides having cyclobutane or phenyl and aromatic sulfonyloxyimide units in the main chain have been synthesized and the photodegradation behavior was investigated in relation with the polymer structure. The polyimides were prepared by condensation polymerization of N-hydroxyl and sulfonyl chloride. The prepared polyimides were stable up to 25$0^{circ}C$ without thermal degradation. It has been found that the photodegradation of polyimides upon irradiation of 254 nm UV light results from scission of N-O bonds or ring opening of imides moiety by spectroscopic measurements. The polyimides were useful as positive working photodegradable polymers. Especially, the positive tone image of polyimide containing a pyromellitic diimide moiety exhibited high sensitivity and resolution.