Abstract The reactions of ionized di-n-butyl ether are reported and compared with those of ionized n-butyl sec-butyl and di-sec-butyl ether. The main fragmentation of metastable (CH 3 CH 2 CH 2 CH 2) 2 O+. is C 2 H 5⋅ loss (85%), but minor amounts (2–4%) of CH 3⋅, C 4 H 7⋅, C 4 H 9⋅, C 4 H 10 and C 4 H 10 O are also eliminated. In contrast, C 2 H 5⋅ elimination is of much lower abundance (20 and 4%, respectively) from metastable CH 3 ...