II-Ⅵ ZnO compound semiconductor thin films were grown on α -Al 2 O 3 (0001) single crystal substrate by radical beam assisted molecular beam epitaxy and the optical properties were investigated. Zn(6N) was evaporated using Knudsen cell and O radical was assisted at the partial pressure of 1 × 10 4 Torr and radical beam source of 250-450 W RF power. In θ -2 θ x-ray diffraction analysis, ZnO thin film with 500 nm thickness showed only ZnO(0002)and ZnO(0004) peaks is believed to be well grown along c-axis orientation. Photoluminescence (PL) measurement using He-Cd ( λ =325 nm) 325 nm) laser is obtained in the temperature range of 9 K-300 K. At 9 K and 300 K, only near band edge (NBE) is observed and the FWHM's of PL peak of the ZnO deposited at 450 RF power are 45 meV and 145 meV respectively. From no observation of any weak deep level peak even at room temperature PL, the ZnO grains are regarded to contain very low defect density and impurity to cause the deep-level defects. The peak position of free exciton showed slightly red-shift as temperature was increased, and from this result the binding energy of free exciton can be experimentally determined as much as 58± 0.5 meV, which is very closed to that of ZnO bulk. By van der Pauw 4-point probe measurement, the grown ZnO is proved to be n-type with the electron concentration( n e ) 1.69 \times10 18 cm 3 , mobility( μ ) ?12.3cm 2 /Vㆍs, and resistivity( ρ ) 0.30 Ω ? cm.