A new bismuth-organic compound containing 1,10phenanthroline (phen) and 2,5-pyridinedicarboxylic acid (PDC) was synthesized and structurally characterized by single-crystal Xray diffraction. The structure consists of 2-D {Bi(phen)(HPDC)-(PDC)} n sheets wherein the PDC ligands bridge metal centers via three unique bonding modes. The 2-D sheets are further connected through strong hydrogen-bonding interactions to form a 3-D supramolecular network. The parent compound displayed yellow photoluminescence in the solid state at room temperature. Doping studies were undertaken to incorporate Eu 3+ into the structure, statistically replacing Bi 3+ in small quantities (1, 5, and 10 mol % Eu 3+ relative to Bi 3+ ). All three compounds displayed characteristic Eu 3+ emission, with total quantum yields as high as 16.0% and sensitization efficiencies between 0.21 and 0.37 depending on the Eu 3+ doping percentage.