Hematoporphyrin (Hp) solutions were subjected to a wide range high intensity (0.2–10.0 GW/cm
2) near-UV laser pulse radiation (
exc=355 nm, pulse duration 30 ps). The formation of stable Hp photoproducts was followed by UV-VIS absorption spectroscopy and liquid-gel column chromatography. As judged by the influence of free radial scavengers, a significant part of the products is assigned to arise from the reaction of Hp with OH · (and H ·) radicals. Using nitroxide radicals (TEMPO and TEMPONE) and the spin trap DMPO the generation of primary transient photoproducts, hydrated electrons (
e
aq
–
), OH · and H · radicals, was studied varying the pulse intensity at a constant absorbed light energy. The results showed that bi-photonic processes are responsible for the observed product generation (different for
e
aq
–
photoejection and OH · (OH ·) formation). A tentative diagram of the Hp excitation routes involved in the present high intensity laser flash photolysis is suggested. According to it, OH · and H · radicals are supposed to be generated in a resonance energy transfer reaction from highly excited Hp
** to water molecules (H
2O sensitization).