Rotherham were 3-1 up by the break as hapless Chester's goals against tally went up to 16 so far.
Alex Rhodes curled a testing free-kick into the area from the right and striker Drewe Broughton headed it down for centre-back Ian Sharps to drive home his first goal of the season.
It stunned the visitors whose miserable start to the season has left them without a goal.
They might have come close to a quick reply after seven minutes when a quick free kick was fed to Kevin Ellison, who spun cleverly but drove his shot wide.
But five minutes later Rotherham broke quickly and Rhodes swung in a dangerous cross from the left but Reuben Reid's header was wide.
Reid who scored in Rotherham's opening day win over Lincoln added his second in bizarre fashion.
Chester though finally their first goal of the campaign after 18 minutes when Ellison pulled one back when he rifled a shot past Andy Warrington after catching out the home defence.
Rotherham struck again after 27 minutes to restore to two-goal advantage with a sweet move.
Jamie Green picked out Reid with a clever angled pass and Reid produced and inch-perfect flick to send Rhodes racing into the area to slot home his shot wide of John Danby.
Chester went close through Ellison and Ryan Lowe in a brighter second half for the visitors, but Reid might have added another for Rotherham.