Abstract The electron impact mass spectra of ten new C 2 ‐symmetric chiral bis(oxazoline) and bis(thiazoline) have been studied. Bis(thiazoline) and bis(oxazoline) possess the same fragmentation mechanism under EI conditions. An unusual fragmentation pathway has been found in the compounds studied. Due to the presence of phenyl group, compounds 6 and 10 undergo a new fragmentation pathway except for the common way as the other eight compounds. Mass analyzed ion kinetic energy spectra experiments and high resolution accurate mass measurement were conducted to confirm the proposed fragmentation pathways.