The present work reports microwave-assisted synthesis of SnO nanoparticles via green route using Psidium Guajava extract. For the enhancement of catalytic activity, nanohybrids of SnO were formulated using different ratios of polyaniline (PANI) via ultrasound-assisted chemical polymerization. Formation of nanohybrids was confirmed via IR and XPS studies. The UV-vis DRS spectra of PANI/SnO revealed significant reduction in the optical band gap upon nanohybrid formation. Microwave-assisted catalytic efficiency of pure SnO, PANI, PANI/SnO nanohybrids was investigated using DDT as a model persistent organic pollutant. The degradation efficiency of PANI/SnO was found to increase with the increase in the loading of PANI. Around 87% of DDT degradation was achieved within a very short period of 12 min under microwave irradiation using PANI/SnO-50/50 as catalyst. The effect of DDT concentration was explored and the degradation efficiency of PANI/SnO-50/50 catalyst was noticed to be as high as 82% in presence of 100 mg/L of DDT. The effect of microwave power on the degradation efficiency revealed 79% degradation using the same nanohybrid when exposed to microwave irradiation for 5 min under 1110 W microwave power. Scavenging studies confirmed the generation of OH, O radicals. The fragments with m/z values as low as 86 and 70 were confirmed by LCMS analysis. Recyclability tests showed that PANI/SnO-50/50 nanohybrid exhibited 81% degradation of DDT (500 mg/L) even after the third cycle, which reflected high catalytic efficiency as well as remarkable stability of the catalyst. This green nanohybrid could therefore be effectively utilized for the rapid degradation of persistent organic pollutants.