In the present work, two new cobalt(III) complex salts [Co(NH3)5N3]SiF6∙2H2O (1) and [Co(NH3)5N3]IO3.Cl.H2O (2) were synthesised. The crystals were grown by the slow evaporation solution technique at room temperature, and their structure was determined by means of single crystal X-ray diffraction studies. Complex salt (1) crystalizes in orthorhombic P212121 space group, with cell parameters a = 8.8969(9) (Å), b = 10.0689(10) (Å), and c = 14.1254(14) (Å). Complex salt (2) crystalizes in triclinic P-1 space group with cell parameters a = 6.8220(9) (Å), b = 7.1709(9) (Å), and c = 12.8742(15) (Å). The band gap values for (1) and (2) have been calculated using Tauc's method, yielding values of 1.72 eV for (1) and 2.51eV for (2). Furthermore, the dielectric constant properties of [Co(NH3)5N3]SiF6∙2H2O (1) and [Co(NH3)5N3]IO3.Cl.H2O (2) have also been studied, and results indicate the high conduction nature of [Co(NH3)5N3]SiF6∙2H2O (1) .