BMI is to start a daily service from Heathrow to the Libyan capital Tripoli on December 1.
British Airways has been the only carrier to serve the route with a daily service since 1999. Libyan Airlines flies twice weekly from Heathrow, while Air Afriqiyah flies daily from Gatwick.
Tickets on the new service are available from today, starting at £265 for a return ticket.
Newspaper reports have suggested the new service is a sign relations between the UK and Libya are improving.
Libyan leader Muammar al-Gaddafi is eager to improve the country's inbound tourism industry.
The North African country also has a booming oil and gas sector that is likely to attract business traffic from the UK.
The country's international reputation was left in tatters after it was held responsible for the bombing of Pan Am flight 103 over Lockerbie in Southern Scotland that killed 270 people in 1988.
There was also controversy last year when the alleged Lockerbie bomber Adbelbaset al Megrahi was released from a Scottish prison and allowed to return home on compassionate ground.
Doctors said al Megrahi had only months to live because of prostate cancer. He is still alive 13 months later.