A new soluble luminescent poly[2-decyloxy-5-(4'-ethoxyphenyl)-1,4-phenylene-vinylene] (DEP-PPV) is prepared by the dehydrohalogenation of 1,4-bis(bromo-methyl)-2-decyloxy-5-(4'-ethoxyphenyl) benzene in this study. The structure and properties of the DEP-PPV are examined by H-1 NMR, FT-IR, UV/VIS, TGA, photoluminescence (PL), and electroluminescence (EL) analyses. The incorporation of a decyloxy substituent in the 2-position of phenylene ring makes the DEP-PPV soluble in organic solvents and eliminates tolan-bis-benzyl structure defects. The energy band gap of DEP-PPV in tetrahydrofuran is 2.36 eV. The PL peak of DEP-PPV solution shifts to higher wavelength as the solution concentration increases. The PL spectrum of the DEP-PPV film shows a peak at 546 nm and the one of the pristine PPV film does at 540 nm. This red shift of PL peak for the DEP-PPV as compared with that for the PPV indicates that the incorporation of a conjugated ethoxyphenyl group on the phenylene ring can increase the conjugation length of phenylenevinylene units in the DEP-PPV. With the DEP-PPV acting as a light-emitting polymer, a device is fabricated with a sequential lamination of ITO/PEDOT/DEP-PPV/Ca/Ag. The EL spectrum of the device shows a maximum emission at 530 nm, which corresponds to the yellowish-green light. The turn-on voltage of the device is about 16 V. Its maximum brightness is 46 cd/m(2) at a voltage of 18 V.