This paper describes a non-contact method to characterize isotropic and anisotropic planar multilayer structures using a genetic algorithm. The method is based on the determination of critical angles, where the maxima of the modulus of transmission coefficient of the structure appear, and which correspond to the generation of guided waves. The optimization process minimizes the error between the reference critical angles and associated amplitudes of the transmission coefficient, with the corresponding estimated ones. The estimation of elastic parameters is demonstrated for acrylic and oak plates as well as for a bi-layered structure composed of oak and a thin layer of gesso. It is shown that to obtain satisfactory optimization results, it is necessary for guided modes of higher order than the zero ones to be taken into account. Results also show that some elastic constants such as C33 and C55 retrieved from the transmission coefficient are very sensitive to the optimization.