In the present paper we are concerned with a numerical analysis of the boundary layer of non-equilibrium dissociated gases over a semi-infinite flat plate with catalytic surface. The method of analysis is basically along with the series-expansion method in terms of the distance from the leading edge along the surface. A straightforward application of the series-expansion method to the problem is shown to result in a solution valid only within a very narrow region near the leading edge. To eliminate this difficulty in the series-expansion method, the temperature involved in the atom-production term has been approximated by the associated frozen temperature, and then a numerical scheme is presented such that any higher order terms in the series solution can be evaluated. In the actual procedure, the truncation error for the resulting solution can be estimated, and the error caused by the approximation for the atom-production term can also be checked if the same procedure is iterated by applying the resulting temperature as the zeroth iterate. The method presented here is applied to the numerical example of high temperature flow of nitrogen over a flat plate surface for a wide variety of surface catalycity and uniform flow velocity. An applicability of the method to the actual problem has been confirmed and the effect of the dissociation-recombination reaction of gases and the catalytic surface reaction is examined on the boundary-layer-flow characteristics; temperature and atom-concentration profiles, and heat transfer to the surface.