The incident happened on the A6094 at Rosewell at about 22:40 on Thursday.
The male rider, 64, and his female passenger, 59, were pronounced dead at the scene. The 26-year-old male driver of the BMW 116 involved in the crash was not seriously injured.
The road has been closed as investigations are carried out. Police have appealed for witnesses.
Two motorcyclists have died after their bike and sidecar was involved in a crash with a car in Midlothian.