Eight solutions containing phosphoric acid with concentrations ranging from 2 mol L-1 to neat acid have been studied by picosecond pulse radiolysis. The absorbance of the secondary radical H2PO4 center dot formed within 7 ps of the electron pulse is observed using pulse probe method in the visible. Kinetic analysis shows that the radicals of phosphoric acid are formed via two mechanisms: direct electron detachment and oxidation by the radical cation of water, H2O center dot+. On the basis of molar extinction coefficient value of 1850 L mol(-1) cm(-1), at 15 ps the radiolytic yield of H2PO4 center dot formation by direct energy absorption is 3.7 +/- 0.1 x 10(-7) mol J(-1) in neat phosphoric acid. In highly concentrated phosphoric acid solutions, the total yield of phosphate radical at 15 ps exhibits an additional contribution that can be explained by electron transfer from phosphoric acid to H2O center dot+. The efficiency of the electron transfer to this strongly oxidizing species in phosphoric acid solutions is lower compared with the one in sulfuric acid solutions. Two explanations are given to account for a relatively low efficiency of H2O center dot+ scavenging in concentrated phosphoric acid solutions.