Luminescent Ln-MOFs (Eu0.075Tb0.925-MOF) were successfully synthesised through the solvothermal reaction of Tb(NO3)3·6H2O, Eu(NO3)3·6H2O, and the ligand pyromellitic acid. The product was characterised by X-ray diffraction (XRD), TG analysis, EM, X-ray photoelectron spectroscopy (XPS), and luminescence properties, and results show that the synthesised material Eu0.075Tb0.925-MOF has a selective ratio-based fluorescence response to Fe3+ or Cr2O72−. On the basis of the internal filtering effect, the fluorescence detection experiment shows that as the concentration of Fe3+ or Cr2O72− increases, the intensity of the characteristic emission peak at 544 nm of Tb3+ decreases, and the intensity of the characteristic emission peak at 653 nm of Eu3+ increases in Eu0.075Tb0.925-MOF. The fluorescence intensity ratio (I653/I544) has a good linear relationship with the target concentration. The detection linear range for Fe3+ or Cr2O72− is 10–100 μM/L, and the detection limits are 2.71 × 10−7 and 8.72 × 10−7 M, respectively. Compared with the sensor material with a single fluorescence emission, the synthesised material has a higher anti-interference ability. The synthesised Eu0.075Tb0.925-MOF can be used as a highly selective and recyclable sensing material for Fe3+ or Cr2O72−. This material should be an excellent candidate for multifunctional sensors.