Studies were conducted to investigate the hypothesis that N-nitrosodimethylamine (NDMA) is a potential disinfection by-product specifically produced during chlorination or chloramination. Experiments were conducted using dimethylamine (DMA) as a model precursor. NDMA was formed by the reaction of DMA with free chlorine in the presence of ammonia and also with monochloramine. We proposed a mechanism for NDMA formation in chlorinated or chloraminated water, which does not require nitrite as in N-nitrosation. The critical NDMA formation reactions consist of (i) the formation of monochloramine by combination of free chlorine with ammonia, (ii) the formation of 1,1-dimethylhydrazine (UDMH) intermediate from the reaction of DMA with monochloramine followed by, (iii) the oxidation of UDMH by monochloramine to NDMA, and (iv) the reversible chlorine transfer reaction between free chlorine/monochloramine and DMA which is parallel with (i) and (ii). A kinetic model was also developed to validate the proposed mechanism.