Thiocyanate (SCN−) exists in various industries and is detrimental to the ecosystem, necessitating cost-effective and environmentally benign treatment. In response to alleviate the bacterial toxicity of SCN−, this study developed a two-stage coupled system by tandem of anammox in reactor 1 (R1) and SCN−-driven autotrophic denitrification in reactor 2 (R2), achieving simultaneous removal of SCN− and nitrogen. The total nitrogen removal efficiency of the coupled system was 92.42 ± 1.98%, with nearly 100% of SCN− elimination. Thiobacillus was responsible for SCN− degradation. The deduced degradation pathway of SCN− was via the cyanate pathway before coupling, followed by the co-action of cyanate pathway and carbonyl sulfide pathway after coupling. Although scaling-up study is needed to validate its applicability in real-world applications, this study contributes to the advancement of sustainable and cost-effective wastewater treatment technologies, being an attractive path for low-carbon nitrogen removal and greenhouse gas emission-free technology.