The Southeast Asia is one of the most important producers of Ni-laterite deposits in the world, attracting more and more attentions in recent years. However, the lateritization processes as well as the enrichment mechanisms of Ni have not been well constrained. Recently, a Ni-rich laterite profile (KPP) was newly found in the Kelurahan Pondidrha area, Sulawesi island, Indonesia. To better understand the lateritization and Ni enrichment mechanisms, in this study, detailed mineralogical and geochemical analyses were conducted on the KPP. The KPP can be divided into bedrock, saprolitic and lateritic layers from bottom to top. The bedrock is serpentinized harzburgite mainly composed of olivine, serpentine and pyroxene, while the saprolitic layer mainly consists of Fe oxides, olivine, serpentine and pyroxene, and the lateritic layer is dominated by quartz and Fe oxy-hydroxides. Nickel is mainly hosted by serpentine in the bedrock and saprolitic layers, but by oxy-hydroxides in the lateritic layer. From the bedrock to the lateritic layer, whole-rock MgO and CaO contents decrease continuously while TFe2O3 contents increase, with TiO2/Al2O3, Zr/Hf and Pd/Pt ratios keeping stable. Combined with whole-rock pH value deceasing from the bedrock to the weathering products, the above results indicate the decomposition of silicate minerals and the formation of Fe oxides/oxy-hydroxides through hydrolysis during in-situ weathering. This led to the release of Ni and its adsorption by secondary minerals (e.g., Fe oxy-hydroxides in the lateritic layer and serpentine in the saprolitic layer). Nickel shows the highest contents in the saprolitic layer rather than the more weathered lateritic layer, indicating the decoupling between the lateritization and the Ni enrichment degrees. This could be due to the enhanced leaching of Ni from the surface under the tropical rainforest climate and the secondary adsorption in the deeper levels. These Ni enrichment features are commonly observed in the Mg-silicate type laterites, which are distinct from the oxide-type showing highest Ni enrichment in the lateritic layer, indicating that lithology played a critical role in controlling the lateritization and Ni enrichment.