A Suzuki-Miyaura coupling reaction between unactivated alkyl halides and lithium alkynylborates was performed using an iron bisphosphine catalyst. The reaction shows high chemoselectivity and is applicable to a broad scope of substrates bearing electrophilic functional groups. A radical probe experiment using cyclopropylmethyl bromide was conducted to investigate the nature of the intermediate in the reaction, showing that an alkyl radical species is generated from the alkyl halide substrate.