A thermally cross-linkable polymer, poly[(2,5-dimethoxy-1,4-phenylenevinylene)-alt-(1,4-phenylenevinylene)] (Cross-PPV), was synthesized by the Heck coupling reaction. In order for the polymer to be cross-linkable, 20 mol% excess divinylbenzene was added. The chemical structure of Cross-PPV and thermally crosslinked Cross-PPV were confirmed by FT-IR spectroscopy. From the FT-IR, UV-Vis, and PL spectral data, thermally crosslinked Cross-PPV was insoluble in common organic solvents. The HOMO and LUMO energy level of thermally cross-linked Cross-PPV were estimated -5.11 and -2.56 eV, respectively, which were determined by the cyclic voltammetry and UV-Vis spectroscopy. From the energy level data, one can easily notice that thermally crosslinked Cross-PPV can be used for hole injection layer effectively. Bilayer structured device (ITO/crosslinked Cross-PPV/PM-PPV/Al) was fabricated using poly(1,4-phenylenevinylene-(4-dicyanomethylene-4H-pyran)-2,6-vinylene-1,4-phenylenevinylene-2,5-bis(dodecyloxy)-1,4-phenylenevinylene (PM-PPV) as the emitting layer, which have HOMO and LUMO energy levels of -5.44 eV and -3.48 eV, respectively. The bilayered device had much enhanced the maximum efficiency (0.024 cd/A) and luminescence (45 cd/m2) than those of a single layer device (ITO/PM-PPV/Al, 0.003 cd/A, 3 cd/m2). The enhanced performance originated from that fact that cross-linked Cross-PPV facilitatse the hole injection to the emissive layer and the injected hole and electron from ITO and Al are recombined in emitting layer (PM-PPV) effectively.