Rare earth europium (Eu(III))-pyromellitic acid (H4L)-1,10-phenanthroline (phen) ternary luminescent complex has been synthesized in polyvinylpyrrolidone (PVP) matrix by precipitation method. The chemical constitution of the complex has been demonstrated as PVP/EuL4/3L(phen)•2H2O by a combination of elemental analysis, inductively coupled plasma-atomic emission spectroscopy (ICP-AES) and Fourier-transform infrared spectroscopy (FT-IR). X-ray diffraction analysis (XRD) has shown that the complex is a new kind of crystal whose structure is totally different from two ligands. The morphology of the complex has been investigated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results have shown that the complex has a rodlike crystal structure and the diameter of the rod is about 400 nm. Thermogravimetric analysis (TG) has indicated that the luminescent complex is thermally stable below 300 °C. Photoluminescence spectra (PL) have revealed that the complex can emit Eu3+ characteristic red fluorescence under ultraviolet excitation.