This study investigates the phase composition, crystal structure, and phase transitions of potassium-substituted copper sulfide (KxCu1.97-xS), focusing on the effects of potassium doping on the material’s properties. Using X-ray diffraction analysis, we identified the structural characteristics of potassium-doped variants, confirming their retention of the monoclinic chalcocite structure (P21/c) with slight modifications in lattice parameters. The incorporation of potassium ions resulted in observable changes in the unit cell dimensions, suggesting enhanced ionic interactions and potential impacts on electronic conductivity. The thermoelectric coefficient, electro-conductivity, and thermoelectric power were also examined, revealing that potassium doping could stabilize certain phases under varying temperature conditions. This work provides valuable insights into the structure-property relationships in copper sulfides, highlighting the potential for tailored materials in thermoelectric applications and other advanced technologies. Future studies will explore the implications of these findings for optimizing the performance of potassium-doped copper sulfides in practical applications.