The sustainability assessment of vinyl chloride process routes was studied by exhaustive identification of all alternative synthetic routes generated from MATLAB software ‘create_reaction set’, and hierarchically assessments of all the identified synthetic routes in terms of available energy (or exergy) dissipation, potential profit and toxicity index. The results showed nine feasible routes for the manufacture of vinyl chloride, although through manual decision fourteen synthetic routes are identified. Assessment using criteria of available energy (or exergy) dissipation showed that eleven synthetic routes are further assessed in terms of other criteria eliminating three routes. Also assessment using criteria of potential profit, synthetic route 8, (Cl2 + 2HCl + C2H4 + 3C2H2--> 4C2H3Cl) with a potential profit of 51₵/lb was considered for further assessment in terms of the toxicity eliminating other synthetic routes. Synthetic route 8 is assessed in terms of the toxicity as the only synthetic route that survived all the scrutiny , hence considered sustainable. Assessment of all the identified alternative synthetic routes render it possible to rapidly screen out process routes that are highly unlikely to be sustainable, at the earliest possible stage, thereby preventing the enormous expenditure required for developing such processes.