The invention discloses a hydroquinone solution separation and purification system, which comprises a distillation kettle, a hydroquinone collection kettle, a distilled water collection kettle, an oil condenser, an oil tank, a first water condenser and a second water condenser, wherein a feeding opening, an air inlet opening, a water steam outlet valve and a hydroquinone steam outlet valve are formed in the top of the distillation kettle; a hydroquinone solution enters the distillation kettle from the feeding opening; the steamed-out water steam flows out from the distillation kettle and is condensed into distilled water through the second water condenser; the distilled water enters the distilled water collection kettle; the steamed hydroquinone gas flows out from the distillation kettle and is condensed into liquid through the oil condenser; the liquid enters the hydroquinone collection kettle; the oil condenser, an oil tank and the first water condenser form a cooling oil circulation pipeline so that the cooling oil flows in a circulation pipeline to be cooled; the first water condenser and the second water condenser share one water cooling system. The invention also discloses a method for separating and purifying the hydroquinone by using the system; a two-stage distillation method is used.