The council, which gets £10.4bn a year from the state to fund adult education and training, will ask a staff member in each of its nine regional offices to take responsibility for championing the cause of voluntary sector service providers.
The ambassadors, who were proposed by the council's voluntary sector advisory group, will receive training to help them better understand the sector. They will also be offered secondments within charities.
The initiative is one of several measures adopted by the council, which has a record of Compact breaches, so as to establish a better relationship with charities.
Other proposals include opening up the commissioning process to ensure that the voluntary sector is more aware of service delivery opportunities.
The council has also promised to standardise the franchise arrangements for charities that deliver services for further education colleges. Voluntary groups have expressed concern that colleges charge widely varying fees for these contracts, which are often not openly costed.
"We are looking at a way forward for how the council will work with the voluntary sector," said Shirley Cramer, chief executive of Dyslexia Action and chair of the advisory group.
"What are the main barriers? How do we break this down and improve the situation so we get the best in a fair and transparent way?
"There is national concern about the number of young people not in education and training, and the advisory group and the council feel that the voluntary sector has a vital role to play in accessing those who are hardest to reach."
The NCVO was cautious about the likely outcome of the LSC's overtures. In January, it wrote to Alan Johnson, Secretary of State for Education and Skills, asking him to intervene and prevent the council taking legal action against an unnamed small charity that provides services on its behalf. The matter remains unresolved.
An NCVO spokeswoman said: "We have heard from several sector professionals about a bullying culture at the skills council towards the sector," she said.
"For the relationship to move from this to the one described in the Compact, we will need to see serious commitment from the LSC. We fully welcome these steps and are keen to see the LSC working closely with the sector to address these issues."