Childcare would be "transformed" under independence with families saving almost £5,000, according to Alex Salmond.
The First Minister is due to visit a soft-play centre in Edinburgh, where he will say that a Yes vote will help parents with childcare costs.
The Scottish Government has committed to giving all three and four-year-olds, and vulnerable two-year-olds, 1,140 hours of childcare a year by the end of the first Parliament in an independent Scotland.
That would be extended to all children from the age of one to school age by the end of the second Parliament, according to the white paper on independence.
The SNP says the plans would benefit around 240,000 children, in contrast to the 100,000 it says will be "pushed into poverty" by Westminster welfare reforms by 2020.
Speaking ahead of his visit in the capital, the First Minister said: "Independence gives Scotland the opportunity to transform childcare.
"We have already made progress - almost doubling the level of childcare Labour provided - but we need to go much further if we are to transform the lives of children and help tens of thousands of women back into work.
"Our independence childcare plan delivers the same number of hours free, high quality nursery childcare as children spend in primary school. That's 30 hours a week for the school term.
"And, the saving to families is huge. Childcare is expensive but with this plan, a parent saves almost £5,000 a year for a one year old and more than £2,000 for each two, three and four year old.
"And that is before you add in the extra income families will be able to earn because they will have enough childcare to allow them to get back to work."
"The contrast with the austerity agenda, public service cuts and increasing child poverty on offer from the No camp could not be clearer."
Labour MSP Jackie Baillie said: "Alex Salmond's attempt to bribe women in Scotland has been completely discredited. The impartial experts at the Scottish Parliament have proved beyond any doubt that his numbers simply don't add up.
"Women in Scotland won't be fooled by this attempt to win votes. Alex Salmond has the power to improve childcare today, but wants to use it as a referendum bribe. It's clear where his priorities lie.
"As part of the UK we can have what the majority of Scots want. We can have more powers for Scotland without taking on all the risks of independence. We should say No Thanks to separation on 18 September."