Donations to charity will be possible through the 8,000 cash machines owned by the Royal Bank of Scotland Group from this week.
The group will be the first to enable charitable donations since the government announced the initiative on giving through ATMs in its Giving White Paper, published last year.
The RBS cashpoints will allow users to donate to one of eight charities and give between £1 and £150.
Donations can be made from all RBS cashpoints from today and from those of NatWest and Coutts, which are part of the RBS Group, from tomorrow.
The charities involved to are Cancer Research UK, Barnardo’s, Oxfam, the RNIB, Age UK, Children in Need and the Disasters Emergency Committee, although this seventh option will be activated only when there is a live DEC appeal.
RBS said it used the Charities Aid Foundation’s Giving Report and Charity Trends Database, and nfpSynergy’s Charity Awareness Monitor to assess the most popular causes and charities.
The current charity selection is for the first 14 months of the initiative. An RBS spokeswoman said this would be reviewed in a year’s time and "may or may not be changed".
RBS would not release any estimates of how much money it expected to be donated, she said.
Steve Lampshire, senior community affairs manager at RBS, said: "More than two billion ATM transactions were made in the UK last year and 25 per cent of those are made through our network, so it’s pretty obvious it is a regular part of most people’s daily lives.
"We know that finances are tight for many people, but if our customers do want to make donations, we want to make the process as easy as possible for them."
A spokeswoman for Link, the ATM network, said an announcement would be made in the next month about when the rest of its 65,000 cash machines, which include those operated by RBS, would allow charitable donations.
Bank Machine said yesterday that users of the 4,000 ATMs it operates across the UK would be able to start donating to charities from July.