Against the grain: The anti‐Markovnikov addition of hydrazines to terminal alkynes in the presence of [TpRh(C2H4)2]/P(2‐furyl)3 (Tp=trispyrazolylborate) as a catalyst system has been developed. N‐alkyl‐ and N,N‐dialkyl‐substituted hydrazines are applicable to this highly regioselective hydrohydrazination, which affords aldimine‐type hydrazine derivatives.