An Fe-catalyzed reductive coupling of unactivated alkenes with β-nitroalkenes has been developed. The reaction proceeds through a radical pathway, with β-nitroalkenes serving as the vinylating reagents and the nitro group being cleaved in the process. Therefore, this method provides a viable synthetic approach to valuable secondary- and tertiary-alkylated styrene derivatives. Furthermore, control experiments were conducted and a plausible mechanism is proposed.