More than 300 individual pieces of content will be included initially, but the range of programmes and formats is expected to expand over time.
This is the first deal overseen by Peter Mercier, who was appointed head of mobile at BBC Worldwide back in June this year.
He said: "O2 is the largest UK operator by subscriber numbers so this is clearly a great deal for us in terms of getting our content in from of consumers and demonstrating to our in-house and indie production partners how BBC Worldwide continues to innovate in the digital media sector."
Graham Riddell, head of strategic content partners at O2 UK, said the programme brands offered by BBC Worldwide are much sought after by its customers.
Riddell said: "We're constantly looking for quality new content that will appeal to our customers and this deal paves the way for access to the wealth of material available from the BBC in a range of different and innovative formats."
Earlier this month, BBC Worldwide announced a global review of the £3m media planning and buying account for its Global Channels business. It is planning to launch new versions of its channels, which include BBC Prime and BBC Food, across Europe, Africa and Asia-Pacific. The review does not affect the UK market.