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In this paper, the plane wave diffraction from a semi-infinite parallel-plate waveguide with five-layer material loading is rigorously analyzed for H-polarization using the Wiener–Hopf technique. The Fourier transform of the scattered field is introduced and boundary conditions are applied in the transform domain to formulate the problem as simultaneous Wiener–Hopf equations, which are solved by the factorization and decomposition procedure leading to exact and approximate solutions. The scattered field in real space is explicitly derived by taking the Fourier inverse of the solution in the transform domain. For the region inside the waveguide, the scattered field is represented by the waveguide TM modes, and the field outside the waveguide is evaluated asymptotically by applying the saddle-point method to obtain a far-field expression. Numerical examples of the radar cross section (RCS) for various physical parameters are presented, and far-field scattering characteristics of the waveguide are discussed in detail.