A new bismuth-organic compound containing 1,10-phenanthroline (phen) and 2,5-pyridinedicarboxylic acid (PDC) was synthesized and structurally characterized by single-crystal X-ray 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 Eu3+ into the structure, statistically replacing Bi3+ in small quantities (1, 5, and 10 mol % Eu3+ relative to Bi3+). All three compounds displayed characteristic Eu3+ emission, with total quantum yields as high as 16.0% and sensitization efficiencies between 0.21 and 0.37 depending on the Eu3+ doping percentage.