This article reviews the mechanical behavior and fracture characteristics that discriminate structural polymers from metals. It provides information on deformation, fracture, and crack propagation as well as the fractography involving the examination and interpretation of fracture surfaces, to determine the cause of failure. The fracture modes such as ductile fractures and brittle fractures are reviewed. The article also presents a detailed account of various fracture surface features. It concludes with several cases of field failure in various polymers that illustrate the applicability of available analytical tools in conjunction with an understanding of failure mechanisms.