A useful wave-optics solution is derived for the Čerenkov mode calculation of optical third-harmonic signals that are generated in a multilayer planar optical waveguide. With this modal solution, the ultimate performance of the planar-configuration frequency tripler, being phase matched in the form of coherent Čerenkov radiation, is predictable. Numerical results are shown for the third-harmonic ultraviolet light generation in a planar glass waveguide loaded by a polydiacetylene Langmuir–Blodgett deposited thin film. Furthermore, the possibility of pronounced activation of the third-harmonic radiation from a glass waveguide pumped by an intense laser beam is suggested through field calculations based on a laser-induced damage model. In addition, loss analysis that includes both one- and two-photon absorptions is made by means of a phenomenological propagation model using coupled rate equations.