The paper presents the studies’ results of chemical composition, structure, and physico-mechanical properties of high-calcium ashes from the Kansk-Achinsk coals (2017-2019 selection). It was found that ash has a complex poly-mineral composition and contains hydraulically active minerals and oxides of СаОfr, β-C2S, CA, C3A, C4AF, C2F, CaSO4. According to the content of CaOfr, MgO does not meet standards’ requirements. The uniformity of the volume change is maintained by the composition with 50% of cement. The structure and hardening kinetics of ash and ash-cement stone compositions, obtained from the test of normal density, were analyzed. It was established that the hardening of compositions with ash from the Kansk-Achinsk coals was largely influenced by ash minerals. An equivalent amount of cement in composite binders cannot be replaced. In order to obtain a positive effect, compositions with ash instead cement of no more than 30% and a part of fine aggregate, without exceeding the ratio of ash: cement = 1: 1, should be used.