The association said that the three-year grant would enable it to work with chairs to build their skills, knowledge and confidence, and to reduce their sense of isolation and help them be more effective.
The association said that under the programme it would consult with chairs and vice-chairs of charities with annual incomes of under £1m about the support they need. It would also run a series of workshops throughout England, offer webinars and online surgeries and open an online discussion forum.
The association said that it hoped to reach about 6,000 chairs and vice-chairs through the programme.
The association already receives funding from the Garfield Weston Foundation to support its work with medium-sized charities and said the latest grant would help it to reach many more charity chairs.
Ros Oakley, executive director at the AoC, said in a statement: "We are delighted that the Big Lottery Fund has not only recognised the key role of the chair and the need to support chairs to undertake the role effectively, but is also making a real investment in making it happen. From what we have learned in our three and half years working with chairs, we know we can make a difference to their confidence and approach to governance. This is a real endorsement of our progress to date."
The association was founded in 2013 to help address the relatively little support chairs of charities receive.