A comparative study of the fracture features, strength and deformation properties of pseudo strain-hardening composites based on alkali-activated slag and Portland cement matrices with polypropylene microfiber was carried out. Correlations between their compositions and characteristics of stress–strain diagrams under tension in bending with an additional determination of acoustic emission parameters were determined. An average strength alkali-activated slag matrix with compressive strength of 40 MPa and a high-strength Portland cement matrix with compressive strength of 70 MPa were used. The matrix compositions were selected for high filling the composites with polypropylene microfiber in the amount of 5%-vol. and 3.5%-vol. ensuring the workability at the low water-to-binder ratios of 0.22 and 0.3 for Portland cement and alkali-activated slag matrices, respectively. Deformation diagrams were obtained for all studied compositions. Peaks in the number of acoustic signals in alkali-activated slag composites were observed only in the strain-softening zone. Graphs of dependence of the rate of acoustic events occurrence in samples from the start of the test experimentally prove that this method of non-destructive testing can be used to monitor structures based on strain-hardening composites.