Different physicochemical properties between Cr(VI) and phenolic compounds pose serious challenges for the effective treatment of co-contamination. This study developed an electrodeless high-flow microwave atmospheric plasma jet for the single-step simultaneous degradation of p-nitrophenol (PNP) and reduction of Cr(VI). Following a 15 min treatment with microwave atmospheric pressure plasma, the removal efficiency of Cr(VI) and PNP reached 97.5% and 93.6%, respectively, whereas that of total organic carbon reached 30.2%. Adding PNP to the solution significantly improved Cr(VI) reduction, whereas PNP degradation increased slightly with Cr(VI). The results indicate that the PNP intermediates significantly affected Cr(VI) reduction. Additionally, long-lived H2O2 and short-lived ·H aided the reduction of Cr(VI) during plasma treatment. The addition of hydroxyl scavengers during treatment implied that ·OH was largely responsible for PNP oxidation. High-performance liquid chromatography–mass spectroscopy (HPLC-MS) revealed that PNP intermediates, including p-nitrocatechol and 5-nitrobenzene-1,2,3-triol, function as Cr(VI) reductants. On the basis of the examined intermediate products, the potential PNP degradation pathway was investigated. The factors that could influence simultaneous dehgradation and reduction, including solution pH, gas velocity, and distance between the plasma outlet and the water surface were researched. Low pH supports Cr(VI) reduction, and the promotion of PNP for Cr(VI) reduction applies to all pH values. The degradation of PNP is insensitive to pH values with or without Cr(VI). The optimal gas velocity for PNP degradation and Cr(VI) reduction was revealed to be 6 L/min. The simultaneous removal of PNP and Cr(VI) benefits from a shorter distance between the plasma outlet and the water's surface.