The present invention provides a process for distillation of styrenes which can be stably operated without loss of energy saving effect, by leading a part or all of low boiling point component vapor from the top to a compressor to use as a heat source for a reboiler and returning the low boiling point components condensed in the reboiler or a mixture of the condensate and a part of the uncondensed vapor to a recycling line of a distillation column.
