ZnO nanostructures were developed on a Si (100) substrate from powder mixture of ZnO and 5 mol% Pd (ZP-5) as reactants by × sccm oxygen pressures(x= 0, 10, 20, 40). DTA (differential thermal analysis) result shows the Pd(5 mol%)+ZnO mixtured powder(PZ-5) is easily evaporated than pure ZnO powder. The PZ-5 mixtured powder was characterized by DTA to determine the thermal decomposition which was found to be at 800℃, 1,100℃. Weight loss(%) and ICP (inductively coupled plasma) analysis reveal that Zn vaporization is decreased by increased oxygen pressures from the PZ-5 at 1,100℃ for 30 mins. Needle-like ZnO nanostructures array developed from 10 sccm oxygen pressure, was well aligned vertically on the Si substrate at 1,100℃ for 30 mins. The lengths of the Needle-like ZnO nanostructures is about 2 μm with diameters of about 65 nm. The developed ZnO nanostructures exhibited growth direction along [001] with defect-free high crystallinity. It is considered that Zn vaporization is responsible for the growth of Needle-like ZnO nanostructures by controlling the oxygen pressures. The photoluminescence spectra of ZnO nanostructures exhibited stronger 376.7 nm NBE (near band-edge emission) peak and 529.3 nm DLE (deep level energy) peak.