Ionic liquids (ILs) have potential applications in many areas of chemical industry because of their unique properties. However, it has been shown that the ILs commonly used to date are toxic and not biodegradable in nature, thus development of efficient chemical methods for the degradation of ILs is imperative. In this work, degradation of imidazolium, piperidinium, pyrrolidinium and morpholinium based ILs in an ultrasound and zero-valent iron activated carbon (ZVI/AC) micro-electrolysis system was investigated, and some intermediates generated during the degradation were identified. It was found that more than 90% of 1-alkyl-3-methylimidazolium bromide ([C
n
mim]Br, nΒ =Β 2, 4, 6, 8, 10) could be degraded within 110Β min, and three intermediates 1-alkyl-3-methyl-2,4,5-trioxoimidazolidine, 1-alkyl-3-methylurea and N-alkylformamide were detected. On the other hand, 1-butyl-1-methylpiperidinium bromide ([C4mpip]Br), 1-butyl-1-methylpyrrolidinium bromide ([C4mpyr]Br) and N-butyl-N-methylmorpholinium bromide ([C4mmor]Br) were also effectively degraded through the sequential oxidization into hydroxyl, carbonyl and carboxyl groups in different positions of the butyl side chain, and then the N-butyl side chain was broken to form the final products of N-methylpiperidinium, N-methylpyrrolidinium and N-methylmorpholinium, respectively. Based on these intermediate products, degradation pathways of these ILs were suggested. These findings may provide fundamental information on the assessment of the factors related to the environmental fate and environmental behavior of these commonly used ILs.