As a result of the high nucleophilicity of the 6p 2 lone pair on the Bi(I) center, bismuthinidene 1 has recently been shown to engage in polar SN2-type reactions with alkyl halides and triflates. Similarly, 1 reacted quantitatively with a range of benzyl (pseudo)halides (Cl, Br, I, OMs) to give benzyl bismuth(III) complexes 5-8 (Fig. ). Cyclic voltammetry analysis of 1 (E1/2 = -0.85 vs Fc 0/+ ) evidences that such C-X cleavages should proceed through a classical SN2 pathway (Ep/2 < -2.0 V vs Fc 0/+ ). On the other hand, the electrochemical behavior observed suggested that 1 could potentially engage in SET oxidative addition processes with alkyl redox-active electrophiles (Fig. ). Accordingly, reaction of 1 with 1 equivalent of tetrachlorophthalimide ester 2 (Ep/2 = -1.1 V vs Fc 0/+ ) cleanly afforded benzyl bismuth(III) complex 9, after SET and fragmentation upon release of CO2, followed by radical recombination. The resulting alkyl bismuth(III) adduct could be fully characterized by NMR, HRMS and single-crystal X-ray diffraction.