The possibility of selective hydrogenation of 5-vinyl-2-norbornene to 2-vinylnorbornane with hydrazine hydrate in the presence of an oxidant (oxygen or air oxygen) and a hydrazine hydrate decomposition catalyst has been investigated. It has been shown that the hydrazine hydrate/oxidant/catalyst system makes it possible to hydrogenate the endocyclic (norbornene) double bond of 5-vinyl-2-norbornene to form 2-vinylnorbornane with a selectivity of up to 95% at the 5-vinyl-2-norbornene conversion above 99%. As catalysts for the oxidative decomposition of hydrazine hydrate, Pd/C and copper salts have been tested. The influence of the conditions of 5-vinyl-2-norbornene hydrogenation to 2-vinylnorbornane on the selectivity of the process and the product yield has been studied. An optimized and preparatively convenient procedure for the selective production of 2-vinylnorbornane has been developed.