The supermarket chain will provide freepost envelopes in all of its 752 stores from next month, in a bid to help the UK meet an EU battery recycling directive by 2012.
Sainsbury's recycling manager James McKechnie said that this was the first scheme of its kind in the UK. He added: 'Most people now use either a mobile phone, an inkjet printer or, at the very least, batteries, so we know this will be of benefit to the environment.'
The company - which is Britain's third largest supermarket chain - said that the scheme would contribute money to Comic Relief, as well as sending unwanted mobiles to developing countries.
The average household uses 21 batteries each year, making up a UK total of 25,000 tonnes annually.
The EU has said that a quarter of all small batteries must be collected for recycling by 2012.