Adria Airways is poised to launch flights to capital Ljubljana in the summer.
The twice-weekly service will get under way on 20 May through 24 October.
Adria will operate the flights on Saturdays and Wednesdays using 86-seat CRJ900 aircraft.
The airline, a member of Star Alliance, becomes the ninth to operate out of Liverpool.
Slovenia package trips will be available through Liverpool Airport Holidays, a new operation set up in partnership with TTG Top 50 agency Myriad Travel.
Paul Winfield, aviation development director at Liverpool airport said: “We are delighted to welcome our latest carrier, Adria Airways, to Liverpool.
"Adria will continue to serve the North West market, with an enhanced product, from Liverpool John Lennon Airport."
