The interaction of a liquid with a solid substrate has been the subject of intense research since the early 1800s. The subject is relevant and very important even today from a basic science as well as technological standpoint. Liquid-phase-sintered oxide ceramics often contain a siliceous glassy layer in the grain boundaries which affect the properties of the ceramic. The wetting of the grain boundaries by the liquid has a strong dependence on the crystallography. While some boundaries are preferably wet, other special boundaries appear to be completely ‘dry’. The presence of the liquid film also affects the faceting behavior of the boundary plane. While several studies have been carried out on these intergranular glass films, many of the basic issues still remain unclear. The development of modern microscopy techniques facilitate the characterization of structure and chemistry at a high spatial resolution. This paper deals with the microstructural examination of two of the important issues involved with these intergranular films, i.e., faceting of grain boundaries in the presence of a glassy phase and the behavior of interfaces between two glassy phases of different compositions.