Europium-doped yttrium picolinate microspheres have been synthesized by a facile aqueous solution method using picolinic acid as complexing as well as structure-directing agents. The synthesized particles are composed of microspheres with europium-doped yttrium picolinate nanohybrids as building blocks which are stacked together driven by mutual interactions of organic components. The formula of undoped hybrid was determined as Y(OH)2(C6H4NCOO)•1.5H2O based on thermogravimetry (TG), elemental analysis and Fourier transform infrared (FT-IR) spectroscopy. The formation of the hybrid microspheres can be explained on the basis of metal-ligand complexation and self-assembly through π-π interactions. Picolinic acid was found to play dual roles as chelating and structure-directing agents for manipulating the particle morphology. The europium-doped yttrium picolinate shows strong red luminescence due to an efficient energy transfer from pyridyl rings to luminescent Eu centers.