A new class of lanthanide mixed carboxylate ligands compounds with formula {[Ln2(phthgly)4(bdc)(H2O)6]·(H2O)4}∞, labeled as Ln3+: Eu (1) and Gd (2) coordination polymers (CP), were synthesized at mild reaction conditions between lanthanide nitrate salts and a solution of N‐phthaloylglycine (phthgly) and terephthalic (bdc) ligands. The (1) and (2) coordination polymers are formed by symmetric binuclear units, in which phthgly and bdc carboxylate ligands are coordinated to the lanthanide ions by different coordination modes. Surprisingly, all organic ligands participate in hydrogen bonding interactions, forming an extremally rigid crystalline structure. The red narrow emission bands from the 5D0 → 7FJ transitions of the Eu3+ ion show a high color purity. The intramolecular energy transfer process from L→Eu3+ ion has been discussed. The experimental intensity parameters (Ω2,4) reflect lower angular distortion and polarizability of the chemical environment around the metal ion compared with other Eu3+ compounds reported in the literature. This novel class of coordination polymer offers a more attractive platform for developing luminescent functional materials for different applications.