A chemical study of the lichen Ramalina siliquosa complex found in Brittany was conducted. Eight chemotypes were considered and their chemical composition was elucidated for the first time by LC–MS analysis. Ten main compounds were identified: conhypoprotocetraric acid (1), salazinic acid (2), peristictic acid (3), cryptostictic acid (4), protocetraric acid (5), stictic acid (6), norstictic acid (7), hypoprotocetraric acid (8), 4-O-demethylbarbatic acid (9), (+)-usnic acid (10) and 22 minor compounds were reported. The MS/MS fragmentation patterns of each compound of R. siliquosa complex were determined and proposed.