The B dopant stability and doping level tunability of ͗112͘ silicon nanowires ͑SiNWs͒ with alkene adsorption are revealed based on first-principles calculations. It is found that the alkenyl chains favor the middle location of ͑111͒ facet, and the B dopants prefer to locate at ͑110͒ facet of the ͗112͘ SiNW. Interestingly, the B doping levels are activated upon an alkene adsorption which introduces an intermediate energy level. This finding sheds light on how SiNWs can achieve effective doping.