Guided waves are now well established for some applications in the non-destructive evaluation of structures and offer potential for deployment in a vast array of other cases. For their development, it is important to have reliable and accurate information about the modes that propagate for particular waveguide structures. Essential information that informs choices of mode transducer, operating frequencies, and interpretation of signals, among other issues, is provided by the dispersion curves of different modes within various combinations of geometries and materials. In this paper a spectral collocation method is successfully used to handle the more complicated and realistic waveguide problems that are required in non-destructive evaluation; many pitfalls and limitations found in root-finding routines based on the partial wave method are overcome by using this approach. The general cases presented cover anisotropic homogeneous perfectly elastic materials in flat and cylindrical geometry. Non-destructive evaluation applications include complex waveguide structures, such as single or multi-layered fiber composites, lined, bonded and buried structures. For this reason, arbitrarily multi-layered systems with both solid and fluid layers are also addressed as well as the implementation of interface models of imperfect boundary conditions between layers.