The electronic properties of silicon, such as the conductivity, are largely dependent on the density of the mobile charge carriers, which can be tuned by gating and impurity doping. When the device size scales down to the nanoscale, routine doping becomes problematic due to inhomogeneities. Here we report that a molecular monolayer, covalently grafted-atop a silicon channel, can play a role similar to gating and impurity doping. Charge transfer occurs between the silicon and the molecules upon grafting, which can influence the surface band bending, and makes the molecules act as donors or acceptors. The partly charged end-groups of the grafted molecular layer may act as a top gate. The doping- and gating-like effects together lead to the observed controllable modulation of conductivity in pseudometal-oxide-semiconductor field-effect transistors (pseudo-MOSFETs). The molecular effects can even penetrate through a 4.92-mu m thick silicon layer. Our results offer a paradigm for controlling electronic characteristics in nanodevices at the future diminutive technology nodes.