A brief history and review of geopolymer technology is presented with the aim of introducing the technology and the vast categories of materials that may be synthesized by alkali-activation of aluminosilicates. The fundamental chemical and structural characteristics of geopolymers derived from metakaolin, fly ash and slag are explored in terms of the effects of raw material selection on the properties of geopolymer composites. It is shown that the raw materials and processing conditions are critical in determining the setting behavior, workability and chemical and physical properties of geopolymeric products. The structural and chemical characteristics that are common to all geopolymeric materials are presented, as well as those that are determined by the specific interactions occurring in different systems, providing the ability for tailored design of geopolymers to specific applications in terms of both technical and commercial requirements.