Understanding the effects of adjuvants on pesticide persistence and penetration in fresh produce is of great significance for optimizing pesticide formulations, managing residues, and ensuring food safety. This study investigated the impact of some common adjuvant products, non-ionic surfactants alkylphenol ethoxylates (APEOs), and crop oil concentrate (COC), on the behavior of systemic and non-systemic pesticide active ingredients (AIs). Surface-enhanced Raman spectroscopy (SERS) combined with liquid chromatography with tandem mass spectrometry (LC-MS/MS) were utilized for accurate analysis of pesticide residue in postharvest spinach leaves and apples. Results indicated that APEOs significantly enhanced the persistence and penetration depth of systemic thiabendazole in both apples and spinach. In contrast, APEOs had negligible impact on the non-systemic phosmet. Furthermore, COC considerably facilitated the penetration of systemic carbaryl in apples but did not aid the persistence of non-systemic thiram when subjected to baking soda soaking. Furthermore, the study developed an effective green washing strategy using common household ingredients to reduce pesticide residues on fresh produce effectively and safely, compared with the washing strategy using a commercial agent. This project is of great significance for providing potent guidance for applying pesticides while minimizing the residues in production agriculture and thus lowering the safety risk to humans.