Holland proved the glue to the Hampshire innings, having been promoted to open, while house-mate Donald provided the flair and fireworks.
The pair smashed an 82-year record for the Ageas Bowl outfit’s fifth wicket as they clubbed 262 together, beating the 235-stand between Gerry Hill and Donald Walker at Portsmouth in 1937.
Hampshire were also boosted by Sam Northeast’s half-century, on the day he was called up for the England Lions squad to face Australia A at Canterbury next weekend.
Warwickshire, who were able to call on Olly Stone for the first time this season, had elected to field without a toss on a green-tinged wicket, under glorious blue skies.
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The fast bowler had been sidelined since January after picking up a back injury while on England duty in the West Indies.
After almost seven months out, it only took 19 balls before he found himself back in the wicket-taking fold as he found Felix Organ’s outside edge, which flew to the second slip.
Stone then didn’t take long to grab a second scalp as Indian Test star Ajinkya Rahane nicked to Will Rhodes as first slip.
With the ball nipping around, and Hampshire 31 for two, Northeast and Holland needed to rebuild.
And they did with a 98-run stand, which negated the new ball and built a strong foundation for the rest of the day’s play.
Northeast fell for 59, after a 54-ball fifty, soon after lunch when Oliver Hannon-Dalby produced a near-unplayable delivery to find an edge behind.
Rilee Rossouw provided a precursor to what was to come with a typically entertaining 34 before he was bowled off his pads by a spearing delivery from spinner Jeetan Patel.
From then on in it was Holland and Donald dominating the Warwickshire bowling.
Holland was boosted up the batting order to replace the out-of-form Oli Soames and Joe Weatherley, who has broken his ankle, as he returned to the side.
He was watchful to reach a 103-ball fifty and continued to climb to three figures while allowing the attacking to be done from the other end.
Holland, who rose to fame in Australia for winning reality cricket TV show Cricket Superstar, eased past his previous best of 58 before poaching a ton in 201 deliveries – bringing up the milestone with a deft sweep.
While Holland grafted for his runs, Donald looked at ease from ball one as he scored at a comfortable run-a-ball, picking up a half-century in 48-balls.
The 22-year-old Welshman, who joined from Glamorgan at the end of last year, then scored his first century since July 2016, his breakthrough double ton, in 103-balls.
But it was his next 20 balls which left the Ageas Bowl with a collective jaw-drop as he moved from 100 to 150 with sixes and boundaries galore.
Holland reached 143, as he showed some attacking intent before he edged Stone behind to end the mammoth partnership.
Donald failed to see out the day when he top edged the final ball of the day to deep square leg - he ended on 173 with five sixes and 21 fours from 143 balls. Hampshire closing on 450 for six.
- ALEX SMITH