One of the most dramatic effects of vibrational and chemical non-equilibrium in hypersonic flows occurs in the bow-shock detachment process in flow over a wedge. This was shown theoretically and in reflected shock tunnel experiments by Hornung & Smith (J. Fluid Mech., vol. 93, 1979, pp. 225–239). In the present work, the effect is first demonstrated by computation of two-dimensional non-equilibrium flows. The effect of the finite transverse extent of the wedge is then studied by three-dimensional computations of non-relaxing flows. An analytical formula is obtained that gives the shock detachment distance of a finite wedge for ideal-gas and equilibrium flows. In the experiment, the finite transverse extent of the wedge competes with the non-equilibrium effects, as each introduces a new length scale. The carbon dioxide and nitrogen flows of the experiment are therefore computed in three dimensions and with two-temperature chemistry accounting for vibrational and chemical non-equilibrium. In the case of nitrogen flow, the agreement between experiment and computation is not good, the experimental detachment distance being larger. A number of possible reasons are quantitatively examined. A conclusive resolution of the discrepancy is considered to require a repeat of the experiment with more accurately characterized conditions. In the case of the carbon dioxide experiments, the computed results agree remarkably well with experiment. This is partially due to the fact that the condition is very close to equilibrium, where the sensitivity of the detachment process to relaxation effects is small. The analytical expression for the dimensionless detachment distance agrees very well with all the three-dimensional computations of non-relaxing flows.