Chemical prestressing is a method of inducing compressive stresses in concrete by using expansive admixtures. Providing that concrete expansion is restrained by internal reinforcement and that sufficient bond strength between concrete and the reinforcement is provided, tensile stresses are introduced into the reinforcement and compressive to the concrete matrix. This approach was invented in the 1940s and currently gains attention again as it might be a suitable method to prestress with non-metallic reinforcement types. Experimental research on thin concrete slabs with carbon textile reinforcement has proven that chemical prestressing contributes to a significant increase in the cracking and ultimate moments. Depending on the amount of expansive admixture used, the cracking moment raised up to about 150% of that of non-expansive concrete slab. Furthermore, more than two times higher deflection at cracking was obtained for prestressed specimens than for non-prestressed ones. Basing on these experimental results and the results of material testing, i.e. shrinkage and expansion measurements, as well as changes in compressive strength and modulus of elasticity, an analytical estimation of the stresses introduced into the slabs is presented. Authors describe the existing approaches to chemical prestressing, in terms of both the mechanism of expansion and the analytical estimation models. These approaches are compared with the obtained experimental results.