We report a new liquid-phase route for alkylation of a Si surface. A Cl-terminated Si(1 1 1) surface was first prepared by UV-assisted chlorination of a H-terminated Si substrate in a PCl5 solution. Alkylation was accomplished by a reaction of the surface Si-Cl groups with n-C4H9Li under reflux condition. We have found that the C4H9-terminated surface exhibits a respectable stability in air. This alkylation technique is not only simple but also effective to reduce carbon and oxygen contamination. as compared to previously reported liquid-phase processes. The Si-C bonds thus formed expectedly serve as a bridge between a rich variety in organic chemistry and advanced silicon technology. (C), 2001 Elsevier Science B.V. All rights reserved.