Insertion of dichlorocarbene (:CCl2), generated by decomposition of the Seyferth reagent PhHgCCl2Br, into the Si-H bond of a tertiary silane to form a Si-CCl2H group is an efficient homogeneous, molecular transformation. A heterogeneous version of this reaction, between PhHgCCl2Br and a silicon (111) surface terminated by tertiary Si-H bonds, was studied using a combination of surface-sensitive infrared and X-ray photoelectron spectroscopies. The insertion of dichlorocarbene into surface Si H bonds parallels the corresponding reaction of silanes in solution, to produce surface-bound dichloromethyl groups (Si-CCl2H) covering similar to 25% of the silicon surface sites. A significant fraction of the remaining Si-H bonds on the surface was converted to Si-Cl/Br groups during the same reaction, with PhHgCCl2Br serving as a halogen atom source. The presence of two distinct environments for the chlorine atoms (Si-CCl2H and Si-Cl) and one type of bromine atom (Si-Br) was confirmed by Cl 2p, Br 3d, and C 1s X-ray photoelectron spectroscopy. The formation of reactive, halogen-terminated atop silicon sites was also verified by reaction with sodium azide or the Grignard reagent (CH3MgBr), to produce Si-N-3 or Si-Me functionalities, respectively. Thus, reaction of a hydrogen-terminated silicon (111) surface with PhHgCCl2 Br provides a facile route to multifunctional surfaces possessing both stable silicon carbon and labile silicon halogen sites, in a single pot synthesis. The reactive silicon halogen groups can be utilized for subsequent transformations and, potentially, the construction of more complex organic silicon hybrid systems.