The Rydberg state reaction H*2+H2→H+3+H+e− was studied by exciting the (X 2∑+g)np,v=0,J Rydberg states with n=30–70 by double resonance excitation via the E,F 1∑+g,v=0,J=1 level and by detecting the product ions or electrons. The results are consistent with the reaction occurring between the ion core of the Rydberg molecule and the ground state molecule, with the Rydberg electron acting as a spectator. Thus, these reactions can be used to provide information on the analogous ion–molecule reactions, and the possibility of using the Rydberg state reactions to study the rotational state dependence of the corresponding ion–molecule reactions is discussed.