In this review, selected applications of CE-MS in recent years have been highlighted for the separation, detection and determination of environmental pollutants and food contaminants in selected samples. Trace analysis by CE-MS of analytes such as low molecular mass amines, nitroaromatics, alkylphosphonic acids, azo dyes, antidepressants, and antibiotic drugs, among others, in air, sediment and water samples have been reviewed. The CE-MS analysis of pesticides such as triazolopyrimidine sulphoanilides, different types of antibiotics (sulphonamides, beta-lactones, quinolones and tetracyclines) and other exogenous compounds such as acrylamide and toxic oligopeptides in food samples has also been reviewed. The review gives details on the fragmentations, where available, that the ionic species exhibit in-source and in ion trap, triple quadrupole and ToF MS analysers. A critical evaluation is also given of these recent CE-MS analytical methods for the separation, detection and determination of trace levels of such pollutants and contaminants with analytical information on the treatment of the samples, CE separation conditions, linearity ranges, LODs and recoveries from the different matrices presented.