Five said that Opie has resigned with immediate effect and will take six months' gardening leave.
It is understood that parent company RTL Group will not replace Opie and that no more personnel changes at Five are immediately on the cards.
The move follows Five's appointment of Dawn Airey as chairman and chief executive of Five to replace Lighting.
Opie said in a statement: "Five is in good health, but Jane's departure and the arrival of Dawn Airey as chairman of Five means that it is time for a change. I would like to wish Dawn all the best in her new role - and assure her that she will be inheriting a highly capable team of creative people. In the meantime, I am confident that Mark White, interim chief executive, will maintain Five's recent progress."
Opie was appointed as Five's managing director of content in October 2006. She was previously managing director of Flextech Television, where she spent 13 years, and where she was also a director of UKTV, Flextech's joint venture with BBC Worldwide.
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