With the evolution of integrated circuits, the transition from polycrystalline silicon to aluminum as the gate electrode has become prevalent due to its inherent advantages. This study considers the impacts of pH, H2O2 and alanine on the aluminum removal rate and surface roughness during chemical mechanical polishing (CMP) with abrasive colloidal silica. Alanine was incorporated as a complexing agent in the polishing slurry in an acidic environment. The mechanistic role of alanine in the aluminum CMP process was investigated with various techniques, including electrochemical tests, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and UV–visible spectroscopy (UV–vis). Additionally, density functional theory (DFT) calculations were used to examine the quantum chemical parameters of alanine and elucidate the complexation mechanism. The experimental results indicated that at an alanine concentration of 1.5 wt%, the Al removal rate was 2124.07 Å min−1 with a surface roughness of 1.33 nm. The interactions between alanine and the aluminum ions (Al3+) yielded soluble Al-alanine complexes, which facilitated corrosion on the Al and enhanced the removal rate.