Mr Henry, the 54 year-old MSP for Paisley South, was promoted to the Cabinet from his post as deputy in the justice department.
It followed the unexpected resignation of Peter Peacock on health grounds.
Mr Peacock has been treated for "symptoms akin to having had a minor stroke", the official statement said. His departure was greeted with universal regret in education circles, and Jack McConnell, the First Minister, paid tribute to his stewardship which had left education "in very good shape".
The new minister lost no time in airing his educational credentials as a former teacher (of business studies and economics at the former Bellarmine Secondary in Glasgow from 1976-79) and as someone who has members of his family working in education; his wife Jacqueline is a former teacher and now works at Strathclyde University, while his daughter Dannielle is a probationer teacher of French in Greenock.
"The immense number of relatives and friends who are teachers will no doubt be taking the opportunity to bend my ear," he told reporters (and a group of pupils from Girvan who happened to be passing through the parliament building when Mr Henry emerged with the First Minister).
Mr McConnell, who had already begun to act almost as his own Education Minister in recent weeks, with a string of high-profile pre-election announcements, may well now be inclined to continue in that role while Mr Henry goes through the arduous process of coming to grips with a complex brief.
The Education Minister has had a chequered professional and political past.
Although he has been a teacher, he actually began his working life as an accountant with IBM and moved out of teaching to work as a welfare rights officer and community care manager in Strathclyde.
Alleged to have been an early member of the hard-left Militant Tendency, he was a Renfrewshire councillor for 15 years, which included a turbulent four-year stint as council leader. Clashes between Labour and the Scottish Nationalist Party became infamous, although Mr Henry was said, even by some in the SNP, to have been less of a scourge of the nationalists than some of his colleagues.
After being elected to the parliament in 1999, he earned his spurs in his three previous ministries of social justice, health and justice. He is regarded as having acquitted himself well in dealing with some contentious and complex policies on drugs, court reforms, knife crime and anti-social behaviour initiatives.
The pattern of Paisley politics has inevitably given him the reputation of being a political bruiser and fixer, but he appears to be well-regarded by friend and foe. "Hugh Henry is bright, was a good council leader in terms of delivering services and he has been a safe, competent minister,"
according to one of his opponents.
The same observer suggests he will be led more by his civil servants than Mr Peacock was, but this is dismissed by a Labour insider who described him as "canny, very bright and imaginative", adding: "He will be no soft touch for officials and will set his own agenda."
What will be on that agenda remains unclear at this early stage. Mr Henry's first words were to commit himself to the mantra that "every child should have the best opportunity in life", an echo of his political origins championing the cause of the disadvantaged.
He is also expected to champion good discipline in schools, which will continue to have the high priority it enjoyed under Peter Peacock. The new minister is a firm believer in Labour's emerging ideas on skills and science academies, excellence in teaching and the curriculum and assessment reforms.
"He was seen as something of a moderniser in the justice field and is not frightened to tackle difficult issues," a colleague says. "He is someone who expects high standards and will be intolerant of second best anywhere."
Peacock says farewell, p20