Despite the discovery of actinide borohydride complexes over 80 years ago, no plutonium borohydride complexes have been structurally validated using single-crystal X-ray diffraction (XRD). Here we describe Pu 2 (H 3 BP t Bu 2 BH 3 ) 6 , the first example of a Pu(III) borohydride complex authenticated by XRD and NMR spectroscopy. Theoretical calculations (DFT, EDA, and QTAIM) and experimental comparisons of metal−boron distances suggest that metal−borohydride covalency in M 2 (H 3 BP t Bu 2 BH 3 ) 6 complexes generally decreases in the order M = U(III) > Pu(III) > Ln(III).