Dr Alan Billings was among six PCCs who signed a letter sent to Theresa May expressing fears over the link between school exclusions and stabbings.
Last year 15-year-old Samuel Baker, who was excluded from school in Sheffield, was stabbed to death in Lowedges by another boy who was also excluded.
A judge said it was ‘another senseless death caused by knife crime’ when he sentenced the killer, then 16, to be detained for two years and eight months.
CRIME: South Yorkshire police chief ‘encouraged’ at Home Secretary’s understanding of knife crime issues
Sheffield Crown Court heard both boys had been involved in cannabis dealing and had been excluded from their respective schools when violence flared last May.
This week, in a letter co-signed by London Mayor Sadiq Khan, police chiefs called for an end to unofficial ‘off-rolling exclusions’ – where pupils are removed from school registers when they are excluded, often to boost exam results.
"Clearly, the way the education system deals with excluded young people is broken," the letter said.
"It cannot be right that so many of those who have committed offences have been excluded from school or were outside of mainstream education.
"That is why the time has come to act urgently. In the first instance, local authorities need powers and responsibilities over all school exclusions.
"Time and again we are hearing how the fragmentation of the education system, and the breaking of the link between schools and local authorities, has led to a lack of accountability, co-ordination and action."
Figures show permanent exclusions in England increased by 56 per cent between 2013-14 and 2016-17.
The letter adds: "There is significant variation by schools as to what will result in exclusion, with many excluded pupils moving between local authority areas and also out of their cities.
"The practice of off-rolling must be outlawed."
The Government is also urged to increase funding for schools to improve early intervention for children at risk of exclusion.
"Our schools are facing significant funding pressures and many interventions for our most vulnerable children are being cut. This cannot be right and schools must have the necessary resources to deliver good interventions and support to those at risk of exclusion," the letter said.
"We are investing in our policing as much as the Government will allow us to do, plus further investing in early intervention projects across our regions.
"Yet so many of the causes of violent crime are out of our control, but in the hands of the Government.
"That is why it is high time the Government matched our ambitions and showed clear leadership on this issue."
West Midlands Police and Crime Commissioner David Jamieson recently described knife crime as a ‘national emergency’, with excluded children most likely to be involved.
He said: "We must do something about that exclusion of children because those children are on almost an immediate path into crime and into violence."
Commissioners for the West Midlands, South Yorkshire, Humberside, Northumbria, West Yorkshire, Leicestershire and South Wales signed the letter.