Zinc complexes with bis[2-(o-hydroxyphenyl) naphtol [1,2] oxazolato ligands (ZnPBO-4) and its derivatives (ZnPBO-S) were synthesized, and luminescent properties of these materials were investigated. Both the fluorescent emission band and electroluminescent emission band were discussed based on their ligand structure differences. The emission band found that it strongly depends on the molecular structure of introduced ligand. It was tuned from 446 nm to 491 nm by changing the ligand structures. Spreading of the π-conjugation in 2-(o-hydroxyphenyl) group gives rise to a blue shift. The EL properties also showed good consistency with their differences of ligand structure. Bright-blue EL emission with a maximum luminance of 3,100 cd/m2 at 12V, current density, 575 mA/m2 was obtained from the organic light-emitting diodes (OLEDs) using ZnPBO-4 as emitting layer. It was also found that the newly synthesized materials were suitable to be used as emitting materials in organic EL device.