Lomefloxacin hydrochloride (LMFX) and sodium salicylate (SS) are important targets for real-time detection due to their widespread uses in daily life; accurate and portable monitoring of LMFX and SS is crucial for human health concerns accordingly. Developing a precise and smart platform for determination of the above analytes remains a significant challenge. Herein, a high-sensitivity platform incorporating a luminescence electrospinning film, self-designed smart-phone app, and portable 3D printing device has been developed to identify LMFX and SS. In this work, two heterometallic coordination polymers with two-dimensional layer structures have been synthesized based on 2,2'-oxidiacetic acid ligand (H2oda), namely, [LnPb(oda)2(CH3COO)]n [Ln = Eu (IMU-1); Tb (IMU-2)]. IMU-1 and IMU-2 were ratio-dependent luminescence probes, which could selectively and sensitively sense with LMFX and SS, respectively. Additionally, the synthesized electrospinning films incorporating IMU-1 and IMU-2 were employed to identify LMFX and SS. Both films could rapidly photograph and color-capture through a portable 3D printing device, along with a self-designed smart-phone app that enabled convenient and quick determination of the concentrations of the above analytes. Remarkably, the mechanism exploration indicated that electron transfer from ligands to analytes affected the antenna effect and further utilized the intrinsic luminescence of analytes along with the luminescence quenching of Ln3+ ions. Furthermore, a strategy for constructing ratio-based fluorescent probes by exploiting the luminescence of analytes and Ln3+ ions in host coordination polymers is proposed. This work provides a new insight by combining luminescence probes, portable devices, and a smart-phone app for real-time detection of drugs and food additives.