The dehalogenation of 2-chloroethanol (2ClEtOH) in the gas phase with and without the participation of catalytic water molecules has been investigated using methods rooted into the density functional theory. The well-known HCl elimination leading to vinyl alcohol (VA) was compared to the alternative elimination route toward oxirane and shown to be kinetically and thermodynamically more favorable. However, the isomerization of VA to acetaldehyde in the gas phase, in the absence of water, was shown to be kinetically and thermodynamically less favorable than the recombination of VA and HCl to form the isomeric 1-chloroethanol (1ClEtOH) species. At the omega B97X-D/cc-pVTZ level of calculation, this species is more stable than 2ClEtOH by about 6 kcal mol(-1) at 298 K, and the reaction barrier for VA to 1ClEtOH is 23 kcal mol t versus 55 kcal mol(-1) for the direct transformation of VA to acetaldehyde. In a successive step, 1ClEtOH can decompose directly to acetaldehyde and HCl with a lower barrier (29 kcal mol(-1)) than that of VA to the same products (55 kcal mol(-1)). The calculations were repeated using a single ancillary water molecule (AT) in the complexes 2ClEtOH_W and 1ClEtOH_W. The latter adduct is now more stable than 2ClEtOH_W by about 8 kcal mol(-1) at 298 K, implying that the water molecule increased the already higher stability of 1ClEtOH in the gas phase. However, this catalytic water molecule lowers dramatically the barrier for the interconversion of VA to acetaldehyde (from 55 to 7 kcal mol(-1)). This barrier is now smaller than the one for the conversion to 1ClEtOH (which also decreases, but not so much, from 23 to 13 kcal mol(-1)). Thus, it is concluded that while 1ClEtOH may be a plausible intermediate in the gas phase dehalogenation of 2ClEtOH, it is unlikely that it plays a major role in water complexes (or, by inference, aqueous solution). It is also shown that neither in the gas phase nor in the cluster with one water molecule, the oxirane path is more favorable than the VA alcohol path. Additionally, a direct conversion of 2ClEtOH to 1ClEtOH through a transition state which resembles a VA molecule in a complex with a chlorine atom and a hydrogen atom on both sides of this planar species was found. This reaction path has also lower activation energy than the conversion to oxirane but not as low as the conversion to VA.