Poly(styrene-b-(ethylene-co-butylene)-b-styrene) (SEBS) is functionalized via radical grafting with 4-vinyl-1-cyclohexene 1,2-epoxide (VCHO) initiated using 2,5-Bis(tert-butylperoxy)-2,5-dimethylhexane. The existence of the epoxide group on the SEBS backbone is evidenced by 1H nuclear magnetic resonance. A size exclusion chromatography (SEC) study reveals some chain coupling, and this phenomenon is limited by controlling the quantities of peroxide and monomer reagents used during the radical grafting. Photo-crosslinking of SEBS-g-VCHO under ultraviolet irradiation in the presence of a cationic initiator is then successfully performed with resultant gel contents higher than 85%. Mechanical properties of SEBS and crosslinked materials are measured by tensile tests on thin films. On the one hand, those tests reveal a significant increase of Young's modulus of the crosslinked materials. On the other hand, the diminution of elongation at break is much more limited; crosslinked materials retain their elastomeric properties with an elongation at break greater than 200%. Finally, the photosensitive SEBS-g-VCHO is used to show the adhesion performance of the photo-crosslinking coating as well as a resin for the stereolithography process.