[en] Concurrently to research conducted on ordinary Portland cement (PC), new types of binders were developed during the last decades. These are formed by alkali-activation of metakaolin or ground-granulated blast furnace slag (GGBFS) and are named, respectively, geopolymers (GP) or alkali-activated slag (AAS). Four different cementitious materials were synthesised: PC, AAS, GP, and a mix GP-AAS and fully compared about their compositions and (micro)-structures. X-ray diffraction has revealed the presence of semi-crystalline C-S-H gel binding phase in PC while AAS, GP and GP-AAS are nearly amorphous. Progressive structural changes have been observed between the different samples by means of infrared spectroscopy, Si-29 and At-27 magic-angle-spinning nuclear magnetic resonance spectroscopy: there is a polymerisation extent of the (alumino)-silicate framework from PC [SiQ(1) and SiQ(2) units] to AAS [SiQ(2) and SiQ(2)(1Al) units] and finally to GP [SiQ(4)(2Al) and SiQ(4)(3Al) units]. Scanning electron microscopy has shown that GP is a homogeneous matrix while the other materials are composites containing GGBFS grains surrounded by a binding matrix. Energy dispersive X-ray EDX analyses (line scans) have shown the absence of formation of any specific phase at the matrix-grains interfaces. (c) 2006 Elsevier Ltd. All rights reserved.