The talks will be overseen by UN envoy to Libya and the UN chief's special representative Bernardino Leon. A press conference is scheduled tomorrow afternoon.
The oil-rich North African country is in tatters with rival governments and parliaments and a slew of militias fighting for territory.
"This is an opportunity the Libyans cannot afford to miss," the EU's foreign policy chief Federica Mogherini said on the eve of the talks.
Mogherini called on the Libyans to "take this opportunity because we are not sure there are going to be other opportunities in the future".
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