ZnO thin films have been grown by metalorganic chemical vapor deposition (MOCVD) and plasma-assisted (PA) MOCVD on c-axis-oriented sapphire (0001) and Si (001) substrates using the novel Zn(2-thenoyltrifluoroacetonate)2·N,N,N′,N′-tetramethylethylendiamine precursor. The structural, morphological, and optical properties of ZnO films have been investigated. The results show that the O2 PA growth results in highly c-axis-oriented hexagonal ZnO thin films also on cubic substrates. PA-MOCVD ZnO films have good optical properties, as inferred by the presence of a sharp and intense exciton in the dielectric function.