In perovskite solar cells, the presence of stress and defects at interfaces promotes performance degradation and poor stability of the devices. The formation of these defects is more prominent in two-step antisolvent-free perovskite film fabrication. This study addresses these challenges by introducing guanidine sulfate (Gua-S) at the tin oxide/formamidinium lead iodide perovskite interface, fabricated without antisolvent under ambient air. Interfacial Gua-S enhanced morphology by forming bonds between uncoordinated Pb2+ ions and I- vacancies at the interface and showed improvement in the crystallinity and quality of the perovskite film. Microstructural stress analysis indicated a substantial reduction in stress, decreasing from 50.6 to 20.72 MPa with the application of Gua-S. Moreover, the Gua-S treated solar cells showed significant improvements and achieved an open circuit voltage of 1.08 V and 22.34% efficiency. Further, electrochemical impedance spectroscopic analysis showed improved built-in potential, carrier lifetime, and charge recombination lifetime for treated devices. The devices retained over 87% of the initial power conversion efficiency after 2000 hours of operation. This comprehensive study addresses the fundamental issues of interfacial stress and defects in perovskite solar cells and demonstrates the efficacy of Gua-S salt in enhancing both the structural and functional aspects of the antisolvent-free device fabrication process.