The effect of Mo addition on microstructural characteristics of a nickel-base single crystal superalloy containing 4 wt% Re was investigated. The γ/γ’ partitioning ratios determined by energy dispersive spectrometer attached to a transmission electron microscope showed that the addition of Mo enhanced the partitioning of Re,W and Cr in the g matrix while decreased the concentration of Ta in the matrix. Synchrotron radiation diffraction was adopted to measure the γ/γ’ lattice misfit at room temperature. The results indicated that Mo addition changed the γ/γ’ lattice misfit towards larger negative as well as increased the tetragonal distortion of the γ lattice. Additionally,Mo addition led to microstructural instability and altered the precipitation behavior of topologically close-packed phases during 1100 C exposure. Instead of precipitating directly from the matrix,the μ phase was observed to be converted from the α phase which precipitated preferentially as a metastable intermediate in the alloy with high Mo content.