Among different silicate systems, CaO−MgO−SiO2 is the one of the most promising due to abundance of reagents, easier fabrication, improved performance, and wide range of application. Analysis of the current literature sources denotes that phase diagram of CaO−MgO−SiO2 system is regularly used by researchers worldwide as constitutive model for synthesis glass-ceramic materials (GCs) possessing an adequate combination of high chemical durability, mechanical and electrical properties. In recent years, materials from this system attracted extra interest for applications in bone tissue repair owing to their ability to induce hydroxyapatite formation in contact with body fluids and to be resorbed in controllable degradation rate. In this brief review diopside containing compositions are specifically discussed. The main goal is to provide critical analysis of the experimental trials directed on synthesis of GC materials in the CaO−MgO−SiO2 system. Glass compositions were analysed through the standpoint of their location in the relevant region, or phase field, within a phase diagram to guide GC production and to make educated choices of compositions and processing parameters. Apart from Introduction and Conclusions this review comprises five consecutive parts. In the first part, constitution of phase diagram of CaO−MgO−SiO2 system is comprehensively discussed with connection to melts’ crystallization path and crystalline phase formation. In the second part, special attentiveness is drawn towards diopside- containing GCs produced from wastes and non-expensive natural raw materials. In this regard and taking into consideration presence of Al2O3 in the majority types of wastes, cross sections of CaO−MgO−SiO2−Al2O3 system with 10, 15 and 20% of Al2O3 are suggested to utilize when anticipating ultimate crystalline phase(s) formation. The following parts of this review are mostly addressed to recent advancement in producing optimized diopside-containing glass–ceramic biomaterials for bone repair as well as innovative sealants for solid oxide fuel cells (SOFC). Likewise, some other active areas of research and application for diopside containing GC compositions are briefly discussed.