Peach is a putrescible fruit thus drastically restricting its postharvest storage life. In recent years, the application of 1-methylcyclopropene (1-MCP) and nitric oxide (NO) in postharvest fruit quality control has received considerable attention and investigative efforts due to the advantages of using relatively low concentrations and short-time treatment duration. In the present study, the effects of various 1-MCP and NO treatments on peach fruit (Prunus persica L. cv. Xiahui-8) stored at 25 °C were evaluated and compared. Results indicated that the combination treatment with both chemical agents (MN) was most effective in postponing peach ripening and preserving fruit quality, followed by 1-MCP and NO treatment alone. We also demonstrated that NO could delay fruit senescence mainly by stimulating antioxidant enzymes, while 1-MCP overly outperformed NO in the treatment of ‘Xiahui-8′ peach in slowing down respiration rate, inhibiting ethylene production, maintaining high firmness and reducing ROS content. NO treatment showed a greater influence on phenolic compounds than 1-MCP especially anthocyanins, flavanones and flavones according to LC/MS analysis. The phenolic change in MN group were highly associated to NO treatment. Through this study we provide informative physiological, biochemical and molecular evidence for the beneficial effects of the combined 1-MCP and NO treatment on peach fruit based on a functional synergy between these two chemical agents.