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A new Ni coordination polymer [Ni(MIP)(BMIOPE)]_n (<b>1</b>) was constructed (BMIOPE = 4,4′-bis(2-methylimidazol-1-yl)diphenyl ether, and H₂MIP = 5-methylisophthalic acid), possessing two-dimensional (2D) twofold parallel interwoven net structure with a 4⁴∙6² point symbol. Complex <b>1</b> has been successfully obtained based on mixed-ligand strategy. The fluorescence titration experiments revealed that complex <b>1</b> could act as multifunctional luminescent sensor to simultaneously detect UO₂²⁺, Cr₂O₇²⁻ and CrO₄²⁻, and NFT (nitrofurantoin). The limit of detection (LOD) values for complex <b>1</b> are 2.86 × 10⁻⁵, 4.09 × 10⁻⁵, 3.79 × 10⁻⁵ and 9.32 × 10⁻⁵ M for UO₂²⁺, Cr₂O₇²⁻, CrO₄²⁻ and NFT. The K_sv values are 6.18 × 10³, 1.44 × 10⁴, 1.27 × 10⁴ and 1.51 × 10⁴ M⁻¹ for NFT, CrO₄²⁻, Cr₂O₇²⁻ and UO₂²⁺. Finally, the mechanism of its luminescence sensing is studied in detail. These results manifest that complex <b>1</b> is a multifunctional sensor for sensitive fluorescent UO₂²⁺, Cr₂O₇²⁻, CrO₄²⁻ and NFT detection.