To economically advantageously recover 1,2-dichloroethane (EDC) by efficiently separating and removing low-boiling component such as chloroprene and 1,1-dichloroethane, benzene and trichloroethylene out of the EDC from a distillate at the top of a separation column for low-boiling materials of an unpyrolyzed EDC in pyrolysis of EDC.

This method comprises distilling and separating components containing chloroprene and having ≤70°C boiling points under a normal pressure at the first distillation column, then feeding bottoms of the first distillation column to the second distillation column installed at the latter step of the first distillation column and distilling the bottoms, removing benzene and trichloroethylene by distilling from the top of the column and recovering EDC from the bottom of the column when pyrolyzing EDC and recovering the EDC from the distillate at the top of the separation column for the low-boiling materials of the unpyrolyzed EDC after separating generated hydrogen chloride and vinyl chloride monomer.