The dissociative excitation of BrCN producing CN(B(2)Sigma (+)) fragment by the collision of He*(2(3)S) was investigated by the collision energy-resolved electron and emission spectroscopy using time-of-flight method with a high-intensity He* beam. The Penning electrons ejected from BrCN and the subsequent CN(B(2)Sigma (+) -X(2)Sigma (+)) emission were measured as a function of collision energy in the range of 90-180 meV. The formation of CN(B(2)Z(+)) is concluded to proceed dominantly via the promotion of an electron from Pi -character orbital, by comparison between the collision energy dependence of the partial Penning ionization cross-sections and the CN(B(2)Sigma (+)-X(2)Sigma (+)) emission cross-section.