Calcium manganite (CaMnO3-δ) has been extensively utilized in many applications due to its unique physical and chemical properties. In this study, the effect of Sr-substitution at the Ca-site on the structural, magnetic, electronic and electrical properties of CaMnO3 manganite perovskites is investigated in detail. The perovskite compounds Ca1-xSrxMnO3-δ (x = 0, 0.25, 0.5, 0.75 and 1) were synthesized through the sol-gel method at 1200 °C. From the patterns of X-ray diffraction, it was observed that all of the synthesized compounds show a pure perovskite phase at room temperature. The refinement results of the perovskite series suggest that a structural transformation from an orthorhombic (Pnma) to a hexagonal (P63/mmc) system occurred for 0.50 < x ≤ 0.75. We note however that the sample with the composition x = 0.50 showed a phase mixture of orthorhombic (Pnma) and hexagonal (P63/mmc). Based on DFT calculations, we have demonstrated the energetic stability of all compounds by negative formation energy and confirmed the semiconductor behavior by the presence of a band gap. The change in the band gap value with the Sr content suggests the potential tuning of the electronic behavior of CaMnO3-SrMnO3 solid solution. Furthermore, as the temperature increases from 300 to 1000 K, the electrical resistivity exhibits a reduction while the Seebeck coefficient (S) shows an augmentation. The negative values of S indicated the n-type-semiconductor nature of all compounds. The obtained values of the activation energy from thermal evolution of resistivity suggested that the electrical transport behavior of all the compounds followed the mechanism of small polaron hopping. Power factor is greatly affected by the Sr amount and reached a maximum value at x = 0.50. Overall, introducing Sr into the CaMnO3-δ matrix improved the power factor and reduced electrical resistivity. According to the obtained results, the studied manganite perovskites could be proposed as suitable materials for photocatalytic and thermoelectric applications.