A general titanium-catalyzed boration of alkyl (pseudo)halides with boranes is reported. The system can successfully suppress the undesired hydrodehalogenation process that prevails using other transition-metal catalysts. The current strategy worked for various alkyl electrophiles, including unactivated alkyl chlorides, with tolerance of reducing functional groups such as ester, alkene, and carbamate. Mechanistic studies reveal a possible radical reaction pathway.