The flights will operate between December 21 and April 2014 with one-way fares starting at GBP34.99.
The airline will use 78-seat Q400 and 88-set Embraer 175 aircraft on the routes. Chambery will be served twice a week, while the other three destinations will be served with weekly flights on Saturdays.
The low-cost carrier currently operates flights from Cardiff to 16 destinations in the UK, Ireland, the Channel Islands and continental Europe, including Belfast City, Edinburgh, Glasgow and Paris Charles de Gaulle.
The airline’s marketing director, Simon Lilley, said: ‘Our four new direct ski routes from Cardiff offer a choice of affordable and particularly attractive ski destinations direct from Wales, saving people valuable time, money and especially the hassle of having to trek to England before they even start their journey.
‘We see these new routes as a natural addition to our network out of Cardiff airport and are confident that these attractive winter destinations can only be positive news for Wales.’
Mr. Lilley added: ‘Flybe will continue to explore all possibilities for expanding our services at Cardiff and we look forward to welcoming our first ‘Welsh snowbirds’ on board in December whether they want to hit the slopes or just simply enjoy a quiet winter getaway.’
Airport chief executive, Jon Horne, said: ‘We have been working closely with Flybe as part of our strategy to bring back a greater choice of flights and destinations to Cardiff Airport and we look forward to exploring further opportunities in this regard.’
The Welsh Government bought Cardiff Airport in March, and had pledged to make it profitable after passenger numbers declined in the recent years.