In this work the synthesis, characterization and photoluminescent and electroluminescent behavior of the [Eu(DBM)3(PTSO)2] complex have been investigated. The emission spectrum of this Eu3+-β- diketonate complex show characteristics narrow bands arising from the 5D0→7FJ (J = 0-4) transitions, which are split according to the selection rule for Cs, Cn or Cnv site symmetries. Triple and doublelayer organic light-emitting diodes (OLEDs) using NPB as hole transporting layer, Alq3 as electron transporting layer and [Eu(DBM)3(PTSO)2] complex as emitting and electron transporting layer were grown and characterized. We found the presence of two concurrent mechanisms for the electroluminescent behavior: (1) the electroluminescence (EL) from the exciton-ligand-Eu3+ ion energy transfer, responsible for the EL narrow bands; and (2) the molecular electrophosphorescence with an initial energy transfer exciton-ligand and posterior intersystem crossing from the excited singlet S1 to the triplet T state followed by molecular phosphorescence (T→S0). The electroluminescent behavior of [Eu(DBM)3(PTSO)2] complex suggest that this complex is promising to applied at Light Conversion Molecular Devices (LCMDs) such as in OLED devices.