Bragg scattering of optical waves in thick gratings at extreme angles, where the scattered wave propagates parallel (extremely asymmetric scattering - EAS) or nearly parallel (grazing angle scattering - GAS) to the grating boundaries, is associated with many unique and practically important resonant phenomena. It has been demonstrated that one of the main physical mechanisms for these resonant phenomena is the diffractional divergence of the scattered wave inside and outside the grating region. This thesis fills the gaps in the theoretical and experimental understanding of Bragg scattering in gratings at extreme angles by investigating EAS and GAS in structures where diffractional divergence of waves is significantly affected by anisotropy and/or non-uniformities of the dielectric permittivity. Unusually high sensitivity of wave scattering in thick periodic gratings to small step-like variations of mean structural parameters at the grating boundaries is predicted and described for the case when the scattered wave (the +1 diffracted order) propagates almost parallel to the front grating boundary (the geometry of GAS). A unusual pattern of strong multiple resonances for bulk electromagnetic waves is predicted and analysed numerically in thick periodic holographic gratings in a guiding slab with mean permittivity that is greater than that of the surrounding media. It is demonstrated that these resonances are related to resonant generation of a new type of eigenmodes in a thick slab with a periodic grating. These eigenmodes are generically related to the grating -- they do exist not if the grating amplitude is zero. A new type of resonant coupling of bulk radiation into the conventional guided modes of a slab with a thick holographic grating is predicted and explained theoretically. It occurs in the presence of strong frequency detunings of the Bragg condition by means of interaction of the strongly non-eigen +1 diffracted order with the slab-grating boundaries. Therefore, it is only in the presence of step-like variations of the mean permittivity at the grating boundaries that this type of resonant coupling can occur. A new method for the analysis of EAS and GAS in anisotropic gratings is developed. This method is based on the consideration of the diffractional divergence of the scattered wave and the two-wave approximation in anisotropic gratings. Special efforts are focused on the analysis of EAS and GAS of extraordinary waves in uniaxial gratings. In particular, it is demonstrated that increasing curvature of the normal surface in the direction of propagation of the scattered wave results in increase of its diffraction divergence and the resonant amplitude. A theoretical model is developed for comparison of the theoretical predictions with data obtained from experimental observations of EAS in a holographic grating written in a photorefractive medium. The developed model is applied for the interpretation of experimental observations of EAS in BaTiO3 photorefractive crystals. Good agreement with the theoretical predictions is demonstrated.