The first-half goal-fest began after just 58 seconds. Alex Rhodes’ free-kick was headed back across goal by Drewe Broughton and Ian Sharps drove home.
Kevin Ellison put the frighteners on Rotherham after seven minutes with a shot that went inches wide before Rotherham doubled their lead in the 14th minute.
Again it was Broughton who headed down and Reuben Reid got a block tackle on Laurence Wilson as he tried to clear and the ball cannoned off Reid past the helpless John Danby.
Chester got their first goal of the season after 18 minutes when Ellison ran through unchallenged to plant his shot wide of goalkeeper Andy Warrington.
But Rotherham were quick to restore their two-goal advantage after 26 minutes when Rhodes rounded off a fine three-man-move involving Jamie Green and Reid before Rhodes applied the finishing touch.
The second half was nothing like as exciting, but Ryan Lowe hit the upright for Chester and Ellison blazed over when well-placed.
At the other end, Reid was a whisker wide and then brought a good save out of Danby but it was lacklustre stuff after the early excitement.