The reactions of laser-ablated B atoms with acetonitrile in 4 K solid neon have been investigated by matrix-isolation infrared spectra, and new products have been identified by 10B, D, and 13C isotopic substitutions and quantum chemical calculations. The side-on complex B-η2-(NC)-CH3 was observed during deposition and isomerized to NCBCH3, CNBCH3, and CNB(H)═CH2, respectively, through C–C bond breakage and hydrogen transfer. For diboron reaction with acetonitrile, the N-end-on complex BBNCCH3 was formed on deposition, which rearranged to HBNC(B)═CH2 and HBNBC═CH2 by λ > 220 nm irradiation. In this reaction pathway, the C≡N triple bond was completely cleaved. The final diboron product HBNBC═CH2 was much more stable than the precursors by 152.0 kcal mol–1 at the CCSD(T)-Full/cc-pVTZ//B3LYP/aug-cc-pVTZ level of theory.