The 21-year-old had been run out for 89 on debut in the previous week’s curtain-raising victory over Fawley.
He followed that up by second top scoring with 67 in a 93-run success against Old Tauntonians & Romsey.
Hambledon, promoted as Division 3 champions last year, would be top of the embryonic league table had they not suffered a close season points deduction.
They were docked 20 points by SPL officials after failing to meet the requisite deadline for all clubs to be Safe Hands compliant.
De Villiers, coming in at No 4, helped opener Dan McGovern add 140 for the third wicket after George Marshall (11) and Henry Glanfield (4) had departed.
McGovern (78) was third out at 163 after hitting nine fours in a 109-ball innings, with De Villiers dismissed after a 86-ball knock containing six fours.
Chris Pratt, out for a duck against Fawley, struck nine boundaries in an almost run a ball 56 as Hambledon posted 268-5 - a total boosted by 20 wides.
When OTs replied, first change bowler Glanfield (3-26) made the breakthrough, removing openers Joe Vaughan and Charlie King.
Middle order pair Nick Newman (39) and Rhys Wathan (30) top scored before George Harding - the sixth and final Hambledon bowler used - dismissed both en route to 3-28.
Safe Hands, meanwhile, is part of the ECB’s safeguarding of children policy, and only Hambledon failed to meet the deadline.
In addition to a points deduction and a £100 fine, the club had to meet two deadlines to become compliant.
Failure to become compliant by last November 4 would have seen them turned down for promotion. Further failure to have become compliant by December 31 would have seen an EGM of all clubs called with the proposal that their SPL membership be terminated.
It obviously never reached that stage, with Hambledon becoming compliant on October 21.