Abstract. Microstructural instability involving the formation of topologically close-packed (TCP) phases is restricted during the alloy development of Ni-based single crystal superalloys. In this study, the effects of alloying elements including Co, Cr, Mo and Ru on the formation of different TCP phases were investigated in a series of single crystal superalloys. Experimental results showed that more additions of Cr and Mo promoted the TCP phase formation, while Co and Ru played a positive role in improving microstructural stability. It is indicated that σ , P and R phases existed with various morphology and compositions in different experimental alloys during thermal exposure at 1100• C. The content of Co, Cr and Mo in those alloys affected the types of TCP phases significantly, while Ru additions showed a negligible effect. R phase was prone to form in alloys containing high level of Co addition. Meanwhile, the ratio of Cr and Mo content had strong influence on the formation of σ and P phases in alloys containing low level of Co addition. The effects of alloying additions on the elemental partitioning ratios between γ and γ phases contributed to their corresponding influence on TCP phase formation.