Highly stereospecific polymerization of isoprene was achieved using borohydridoneodymium complexes. In combination with stoichiometric amounts of dialkylmagnesium, Nd(BH4)(3)(THF)(3) (1) and Cp*'Nd(BH4)(2)(THF)(2) (2) (Cp*' = C(5)Me(4)nPr) afford very efficient catalysts. The activity reaches 37300 (g of polyisoprene/mol of Nd)/h. Half-lanthanidocene 2 gives rise to polyisoprene, 98.5% trans-regular, the highest content yet described for a homogeneous organometallic catalyst. NMR experiments argue for the formation of bimetallic Nd(mu-BH4)Mg active species.