Penning ionization of 2-bromothiophene and 3-bromothiophene by collision with He*(2(3)S) metastable atoms is studied using two-dimensional (collision-energy and electron-energy-resolved) Penning ionization electron spectroscopy. Some satellite bands correlated with ionic states of pi orbitals are observed in Penning ionization electron spectra. Collision energy dependence of partial ionization cross sections indicates that attractive interactions of the He* out-of-plane approach respective to the thiophenyl ring including bromine atom are much stronger than those of the in-plane approach. Substitution of the bromine atom holds the sequence of magnitude of attractive interaction for the out-of-plane approach pi(2) > pi(3) > pi(S) which was previously observed for thiophene. Different substitution sites lead to the change of Penning ionization activity of the in-plane lone pair orbital of the bromine atom, which is interpreted as a result of intramolecular orbital interactions.