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A range of dialkenylmagnesium compounds ([CH2═CH(CH2)n]2Mg; n= 1–6) were synthesized and used as chain transfer agents (CTA) with either (C5Me5)2NdCl2Li(OEt2)2(1) or [Me2Si(C13H8)2Nd(BH4)2Li(thf)]2(2) neodymium precursors for the polymerization of ethylene. In all cases, the systems followed a controlled coordinative chain transfer polymerization mechanism. The intramolecular insertion of the vinyl group on the CTA in growing chains is possible and led to the formation of cyclopentyl, cyclohexyl, and possibly cycloheptyl chain ends. While the production of cyclopentyl- or cyclohexyl-capped polyethylene chains can be quantitative (n= 2–5), the integrity of this double bond can also be kept if nis higher than 6. In comparison to 1/CTA catalytic systems, 2/CTA catalytic systems showed a higher propensity to produce cycloalkyl chain ends. This was ascribed to the lower steric demand around the active site, as shown by DFT calculations. In addition, the formation of bis(cyclopentylmethyl)magnesium from dipentenylmagnesium using a catalytic amount of 2was shown.