A series of novel heterometallic rare-earth chloroterephthalate metal–organic frameworks with the general formula (Tb_xGd_1−x)₂(Cl-1,4-bdc)₃·5H₂O (x = 0–1) were synthesized via direct precipitation from aqueous solutions. The structural and photophysical properties of these compounds were studied in detail. All compounds exhibit bright luminescence upon UV excitation into the ligand absorption band due to an efficient antenna effect. The photoluminescence quantum yield shows a non-monotonic dependence on the concentration of the terbium ion with a maximum value of 71% achieved for the compound containing equal molar fractions of the lanthanide ions. The (Tb_0.5Gd_0.5)₂(Cl-1,4-bdc)₃·5H₂O sample was evaluatedfor its utility in both qualitative and quantitative analysis of selected metal ions and in latent fingerprint development. It was shown to enable the detection of Cr(III), Fe(III), and Cu(II) ions through luminescence quenching, with the emission intensity being concentration-dependent. This behaviour highlights the compound’s potential as a basis for analytical protocols and materials aimed at the quantitative determination of these metal ions.