Chemical mechanical planarization (CMP) has found extensive application in the fabrication of micro-electro-mechanical systems (MEMS). Nickel and Nickel based alloys are known to possess favorable properties that make them promising candidates to realize movable structures for MEMS applications. The development of CMP slurry chemistry for Ni that provides good CMP performance is the key in enabling CMP technology for Nickel based MEMS device fabrication. Unfortunately, very little work has been reported in terms of the electrochemical interaction of Ni with various CMP slurry constituents such as oxidizers, complexants and inhibitors. In this study, CMP of nickel was performed using H2O2 as oxidizer and alumina particles as abrasives. Electrochemical techniques were used to investigate the dissolution/passivation behavior of high-purity Ni under static and dynamic conditions in slurries at pH 4 with the addition of oxidizer, complexing agent and nickel salt. The affected surface layers of the statically etched Ni-disc were investigated using X-ray photoelectron spectroscopy (XPS). The Ni removal rate increased with the addition of oxidizer and further increased with the addition of complexing agent and nickel salt. The electrochemical results indicate that the surface chemistry and electrochemical characteristic of Ni play an important role in controlling the polishing behavior.