Ministers have also pledged to work better together across government departments to support care leavers and improve internship opportunities.
The funding has been announced to coincide with annual awareness raising campaign National Care Leavers' Week (24-31 October).
The additional money includes £10m for the Staying Put scheme, which allows those in foster care to continue living with their carers until they are 21.
This follows criticism of the scheme by campaigners that it is failing to ensure more looked-after children benefit from the policy.
Ofsted figures published in April revealed that the proportion of eligible looked-after children accessing the arrangements fell from 54 per cent in 2015/16 to 46 per cent in 2016/17.
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