A new europium coordination polymer [Eu(2,3′-oba)(2,3′-Hoba)(IP)]n (Eu-CP) has been synthesized by hydrothermal reaction using 2,3′-oxbis (benzoic acid) (2,3′-H2oba) and 1H-imidazole [4,5-f] [1,10]-phenanthroline (IP). The semi-rigid ligand 2,3′-H2oba and large rigid ligand IP form a 1D chain structure of the Eu-CP, which is further stacked into a 3D supramolecular architecture through C–H⋯O and O–H⋯N hydrogen bonding. Below 400 °C, the Eu-CP does not decompose. It shows good chemical stability in common solvents and aqueous solutions with pH in the range of 3–12. The Eu-CP emits strong red luminescence, attributed to the 5D0→7FJ (J = 0–4) transitions of the Eu3+ ion. The luminescence quantum yield and lifetime are 61% and 0.94 ms, respectively. The Eu-CP has a broad absorption in the range of 200–400 nm, with a maximum excitation wavelength of 365 nm. Furthermore, Eu-CP is used as a sensor for the detection of PO43−, dimetridazole (DTZ), and nitrofurantoin (NFT) in aqueous systems, and NFT in biological samples (calf serum) based on the luminescence quenching effect. Notably, luminescent Eu-CP@film was prepared for sensing PO43−, NFT, and DTZ, which can be reused more than 20 times, facilitating a visually simple and rapid online detection platform. In addition, we also studied the luminescence quenching mechanism of Eu-CP by analytes.