At times the teams were closer than the four-tier difference in leagues might suggest, but a brace apiece for Josh Law, Andy Todd and Liam Hearn was added to by a seventh goal from Paul Clayton as Alfreton pulled away in the last 20 minutes.
Law opened the scoring on 14 minutes, having started the move himself on the half way line.
Law's pass through to Hearn took a helpful deflection off Sam Kellogg and, after sprinting down the left, Hearn's cross was swept home by Law from 10 yards.
Holbrook's best chance of the first half came on 19 minutes when Karl Demidh broke from a lucky rebound off Aden Flint only to blast his shot beyond the back post.
Nine minutes later from a second corner in quick succession Shaun Roulston headed wide for the Brookies.
Alfreton gained breathing space with their second goal arrived in the 33rd minute when visiting keeper Damien Clark failed to hold a Law cross from deep right and Hearn rammed the ball in from close range.
Nine minutes after the break Holbrook clearly rattled the hosts when Roulston planted a firm header from a Dave Moon corner beyond keeper Paddy Gamble to make the score 2-1.
That gave the visitors a lift and Demidh went close six minutes later when he fired into the side-netting from 25 yards.
A third goal for the Reds on 63 minutes settled the nerves, after Todd converted an Ian Ross free-kick at the back post - despite the offside flag initially going up.
A frantic three-minute spell ,commencing in the 71st minute ,produced two penalties and three goals, with Flint triggering the sequence of events by tripping Joe Kellogg as he headed for the by-line from Aaron Johnson's cross.
Gavin Whitehead hammered the spot-kick which Gamble parried, only for the penalty-taker to follow up and cut the score back to 3-2.
However straight from the re-start Paul Clayton's by-line cross was turned in at the back post by Todd.
Law then ran onto a Hearn cross only to be upended by the keeper, with Law burying the penalty for 5-2.
Five minutes he returned the compliment by setting up Hearn to score with a strong angled drive after a neat side-step.
Clayton stretched to hook in a cross at close range from the left by Ross with five minutes remaining, with the referee bringing an early conclusion to the proceedings by blowing the final whistle barely into the 90th minute.
ALFRETON: Gamble; Hall, Roma, Flint, Pell (Wilson 67 mins), Burke, Law, Lloyd (Ross 61 mins), Reeves (Clayton 54 mins), Hearn, Todd. Sub not used: Howell.
HOLBROOK: Clark; Whitehead, Thorp, Broadhurst, Roulston, J. Kellogg, Hind (Johnson 45 mins), S.Kellogg, Demidh, Moon, Ashdown (Sadler 71 mins). Subs not used: Hallsworth, Cooper, Mather.
ATTENDANCE: 183.