Earlier, the chairman of the National Transitional Council (NTC) said the country did not need outside help to maintain security.
The news came as fighters loyal to the council approached the pro-Gaddafi stronghold of Sirte from east and west.
The town's defenders have been given until Saturday to surrender.
'Special case'
Libya's deputy representative to the UN, Ibrahim Dabbashi, told the BBC that the situation in Libya was unique.
"They [the UN] put the possibility of deploying peacekeepers on the ground but in fact the Libyan crisis is a special case.
However, Mr Martin said the UN did expect to be asked to help establish a police force.
"We don't now expect military observers to be requested," he said after a meeting of the UN Security Council.
"It's very clear that the Libyans want to avoid any kind of military deployment of the UN or others," he said.
Mr Martin added that one of the greatest challenges for the UN would be helping the country prepare for democratic elections.
"Let's remember [...] there's essentially no living memory of elections, there's no electoral machinery, there's no electoral commission, no history of political parties, no independent civil society, independent media are only beginning to emerge in the east in recent times.
"That's going to be quite a challenge, sort of organisationally, and it's clear that the NTC wish the UN to play a major role in that process."
UN Secretary General Ban Ki-moon has said that growing humanitarian shortages in Libya demand urgent action and appealed to the security council to be "responsive" to requests from the transitional authority for funding.
Though stockpiles of medical supplies and food stashed away by the government were found over the weekend, water supplies are short.
"An estimated 60% of Tripoli's population is without water and sanitation," he said. The EU's humanitarian office says that pro-Gaddafi forces are responsible for cutting supplies.
Ultimatum
On Tuesday, the UN Security Council let Britain release 1.86bn dinars ($1.55bn; £950m) in frozen assets to buy aid for Libya but an attempt by France and Germany to release an additional $8.6bn remains blocked.
Diplomats said that Russia was holding up Germany's request to release about 1bn euros ($1.4bn) in seized assets and France's move to unfreeze about five billion euros ($7.2bn) to buy humanitarian aid, Agence France Presse reports.
As anti-Gaddafi fighters converge on his birthplace of Sirte, interim leaders gave the town's defenders an ultimatum, telling them that they had until Saturday to surrender or face military force.
Also it has emerged that Col Gaddafi's wife and three of his adult children fled to neighbouring Algeria in the early hours of Monday morning.
Though Col Gaddafi's whereabouts remain unknown, with suggestions he may be in Sabha, Sirte or Bani Walid, the deputy head of the NTC, Ali Tarhouni, said they have a good idea of where he is and are confident that they will catch him.
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