Agricultural soil contamination by potentially toxic elements (PTEs) such as arsenic (As) and cadmium (Cd) poses a serious threat to food security. Immobilization serves as a widely used approach for the remediation of PTEs contaminated soils, nevertheless, the long-term effectiveness for the simultaneous immobilization of both cations and oxyanions remains a challenge. In order to effectively enhance the synergistic immobilization effect of soil As and Cd contaminated by multiple elements and improve the ecological environment of farmland. In this study, a typical polluted tailings area farmland was selected for situ immobilization experiments, and biochar was prepared from cow manure (CMB), rice straw (RSB), and pine wood (PWB) as raw materials. On this basis, the pristine biochar was modified with ferric chloride (F), potassium permanganate (K), magnesium chloride (M), and aluminum chloride (A), respectively. Furthermore, the immobilization effect of modified biochar on As-Cd and the stress effect on soil respiration were investigated. The results showed that CMB and RSB reduced the bioavailability of heavy metals, potassium permanganate has strong oxidizing properties, and the strong oxidability of potassium permanganate stimulated the generation of more oxygen-containing functional groups on the surface of biochar, thereby enhancing the adsorption and complexation effect of modified materials on As and Cd. Among them, the extracted Cd concentration of Diethylenetriamine pentaacetic acid (DTPA) in KCMB and KRSB in 2020 decreased by 8.23–43.12% and 9.67–35.29% compared to other treatments, respectively. Meanwhile, the KCMB and KRSB treatments also reduced the enrichment of As and Cd in plant tissues. In addition, the dissolved organic carbon (DOC) content in KCMB treatment was relatively high, and the carbon stability of the material was weakened. Simultaneously, the soil respiration emission of KCMB treatment was increased by 5.63% and 11.93% compared to KRSB and KPWB treatments, respectively. In addition, the structural equation also shows that DOC has a large positive effect on soil respiration. In summary, the KRSB treatment effectively achieve synergistic immobilization of As-Cd and provide important guiding significance for green and low-carbon remediation of polluted farmland.