Nonlinear kinetic parameter estimation plays an essential role in kinetic study in reaction engineering. In the present study, the feasibility and reliability of the simultaneous parameter estimation problem is investigated for a multi-component photocatalytic process. The kinetic model is given by the L-H equation, and the estimation problem is solved by a hybrid genetic-simplex optimization method. Here, the genetic algorithm is applied to find out, roughly, the location of the global optimal point, and the simplex algorithm is subsequently adopted for accurate convergence. In applying this technique to a real system and analyzing its reliability, it is shown that this approach results in a reliable estimation for a rather wide range of parameter value, and that all parameters can be estimated simultaneously. Using this approach, one can estimate kinetic parameters for all components from data measured in only one time experiment.