We report the first observation of the decays B^{0}→pΛ[over ¯]D^{(*)-}. The data sample of 711 fb^{-1} used in this analysis corresponds to 772×10^{6} BB[over ¯] pairs, collected at the ϒ(4S) resonance by the Belle detector at the KEKB asymmetric-energy e^{+}e^{-} collider. We observe 19.8σ and 10.8σ excesses of events for the two decay modes and measure the branching fractions of B^{0}→pΛ[over ¯]D^{-} and B^{0}→pΛ[over ¯]D^{*-} to be (25.1±2.6±3.5)×10^{-6} and (33.6±6.3±4.4)×10^{-6}, respectively, where the first uncertainties are statistical and the second are systematic. These results are not compatible with the predictions based on the generalized factorization approach. In addition, a threshold enhancement in the dibaryon (pΛ[over ¯]) system is observed, consistent with that observed in similar B decays.