The appointment, which was made without a pitch, follows last week's news that CHI and BT had agreed to part because of conflict. TalkTalk poses a credible threat to BT and, as such, presents a direct conflict of interest to any BT agency.
Johnny Hornby, the managing partner at CHI, said: "We really enjoyed working with BT and are proud of the campaign that we produced. But, given that we couldn't work with both companies, Carphone Warehouse, as our founding client, would always have our loyalty."
The agency is not expected to produce a campaign for TalkTalk for the next few months, as it is still in the process of completing its work on BT Yahoo!
Chime Communications' Will Pond-Jones Collective is the incumbent on the TalkTalk business - it created the £1.5 million launch advertising for the telecoms company starring Maureen Lipman, a former face of BT.
TalkTalk has relied heavily on literature carried in the Carphone Warehouse's 470 UK stores and its website to raise awareness of its services.
However, the company is expected to raise its above-the-line budget next year in an attempt to take a more substantial slice of BT's fixed-line customers.
TalkTalk was launched in February and undercuts BT prices by about 30 per cent. It has signed up 200,000 customers to date.
Max Alexander, the managing director of Carphone Warehouse Telecoms, said: "We know CHI well and look forward to a happy and fruitful relationship."