The former Something for the Weekend hosts will move to the channel in March to host new show Sunday Brunch.
"We're chuffed to be joining Channel 4," Lovejoy and Rimmer said in a statement. "We have a great laugh working together and we're very pleased we can continue that in our new home."
Channel 4's head of formats Dominic Bird, who commissioned the programme, added: "Simon and Tim have brilliant on-screen chemistry and their partnership will be at the heart of Sunday Brunch. They're a great fit for Channel 4 and we can't wait to get going on the new show."
Promising a mix of celebrity guests, cookery and "wit, chat and banter", former Something for the Weekend production company Princess Productions will make Sunday Brunch for Channel 4.
Henrietta Conrad has been named as the show's executive producer.
It was previously reported that ITV had opened talks with Princess about launching a similar format to Something for the Weekend on one of its channels.
Something for the Weekend was cancelled earlier this year after a run of almost six years on the BBC.
An online campaign to save the show from the axe attracted support from celebrities including scientist Professor Brian Cox and actress Lisa Faulkner.