The appointment is aimed at showing that the opposition Syrian National Coalition can administer large swathes of captured territory where there is now a power vacuum.
The meeting in Istanbul on Monday and Tuesday follows a push by Britain and France to lift an EU embargo on supplying arms to the rebels fighting President Bashar al-Assad's regime.
However, the decision to name a prime minister and form an interim government is opposed by some opposition figures, who favour the creation of an executive body with limited powers to administer rebel-held territory.
The Coalition list includes virtual unknowns, as well as some prominent members of the opposition.
Former agriculture minister Asaad Mustapha, economist Osama Kadi and former communications executive Ghassan Hitto are believed to be leading the pack.
The meeting is being held with the conflict -- which has killed about 70,000 people and forced millions from their homes according to UN figures -- now in its third year.
"There is a real need in the liberated areas for better administration of daily life," Damascus-based activist Matar Ismail told AFP.
"There should be a civilian authority that acts as an alternative power to the Assad government."
Last week, Britain and France pushed for the EU to lift an arms embargo to allow the supply of weapons to the opposition, but other member states remain cautious, fearing a further escalation of the conflict.
"If we want to achieve a political solution, we must change the military situation on the ground and the rebels must have weapons to fight against the (regime) planes attacking them," French Foreign Minister Laurent Fabius said Sunday.
"Bashar does not want to move. If this continues, not only will there be more deaths, but the risk is that it is the most extreme, meaning Al-Qaeda, will eventually take over," he said on French television.
-- Revolutionary credentials --
Syrian opposition members said they wanted a good administrator with revolutionary credentials for the post of premier, although nations backing the rebels, including Qatar and Saudi Arabia, are also likely to influence the choice.
"The prime minister must be a man who is completely with the revolution, and it is better that it be someone who was in Syria until recently, not someone who has lived abroad for a long time," opposition figure Haytham al-Maleh said.
"The next prime minister won't be chosen on the basis of whose name is most circulated in the media, but on the basis of who is best able to lead a government that takes care of the Syrian people and addresses their most pressing needs," added Ahmed Ramadan, a member of the Coalition.
Aleppo-born Kadi, founder of the Syrian Centre for Political and Strategic Studies in Washington, is favoured for his technocratic background, as is Hitto, who has lived in the United States for decades, obtaining degrees in computer science and business.
Mustapha, born in Idlib in 1947, brings experience as a minister for eight years under former president Hafez al-Assad. "If what's wanted is a technocrat then perhaps Osama Kadi will win. And if the choice is based on who has experience and is the most capable politically, it will be Asaad Mustapha," Ramadan told AFP.
"The latter has good experience... and he has been close to the revolution from its beginning and is respected."
At least one potential candidate, Christian dissident Michel Kilo, has already made clear he will not be standing, and neither former Syrian National Council head Burhan Ghalioun nor defected ex-premier Riad Hijab appears on the current list.
Ramadan said the Coalition was expected to hold an initial vote, followed by a run-off between the top two candidates.
Meanwhile, Coalition members speaking to AFP on condition of anonymity said those opposed to creating an interim government want dialogue with the regime and the formation of a government composed of regime and opposition members.
That is believed to be Washington's preference, although Turkey and much of the Arab League favour an interim government. Opposition supporters on the ground see the vote as an important opportunity to create a real alternative to the Assad government.
"An interim government will also bring the exiled opposition into direct contact with the people. So even if we haven't elected them, we can hold them accountable for their errors. Overall, I am hopeful," Ismail said.