New support is to be given to struggling families under a £30 million government programme focused on helping parents to find work.
The next phase of the Troubled Families Programme will aim to forge better links between disadvantaged families and Jobcentres.
Ministers said there was a "profound" affect on children if their parents were unemployed and had other problems.
A new analysis published by the government showed that children in workless families were almost twice as likely not to reach the expected level at all stages of their education.
Three-quarters of children from families where no one worked failed to reach the expected level at GCSE, compared with about half of children in lower-income working families.
An estimated 300,000 workless families are potentially affected by conflict between parents, while children's emotional, behavioural and educational success are strongly influenced by their parents' relationship.
Work and Pensions Secretary Damian Green, said: "I don't want any child to be defined by the circumstances of their birth. Every child should benefit from a strong relationship between their parents – whether they are together or separated.
"Today marks the start of new support to help families overcome the problems they face to make sure that every child can go as far as their talents will take them."
The government said it would aim to reduce parental conflict through an "innovative" new programme to support interventions delivered by specialist organisations.
Alison Garnham, chief executive of Child Poverty Action Group said: "Investment in relationship support is of course welcome but all the evidence shows lack of money is the biggest stress factor for families and we're about to see that intensify as the Government ploughs on with social security cuts brought in by its predecessor.
"The freeze on benefits and the cuts coming in this week for working and non-working families are what will cause struggling households the biggest pain."