In seeking prostaglandin F(2α) (PGF(2α)) photoaffinity probes possessing both an efficient, photoactive cross-linking substituent and a radiolabel of high specific activity, the synthesis and binding affinity of PGF(2α) C-1 esters in which the alcohol component possessed either an aryl azide or a perfluorinated aryl azide was investigated. These derivatives showed great promise due to their ability to compete for the binding of [3H]-PGF(2α) in both a luteal membrane binding assay and in a whole luteal cell binding assay. Identification of the C-1 site in PGF(2α) as a site for modification of the PGF(2α) molecule with photoactive alcohol derivatives represented a logical step toward the goal of developing a useful PGF(2α) photoaffinity probe.