The latest revelations again raised questions about allegations of conflict of interest targeting the envoy, Bernardino Leon, that may compromise the preliminary deal for Libya that he has negotiated.
In a statement, Leon said that the UAE, Qatar, Turkey and Egypt "have consistently supported UN peace efforts" in Libya and stressed the need to be "extremely cautious" about the reports.
"I have decided to request a full clarification of the issue, including from the United Arab Emirates authorities as I take time to reflect on the next steps in my professional career," said the Spanish diplomat.
The envoy in July accepted a high-paying position as the first director of the government-funded Emirates Diplomatic Academy in Abu Dhabi just as he was negotiating the final draft of the power-sharing deal.
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Leon's controversial appointment was announced last week, but the UAE's alleged role in supplying weapons came to light on Thursday.
The New York Times reported that the UAE sent weapons to Libya in violation of a UN arms embargo to counter regional rival Qatar, which was arming Islamist militias.
Other emails cited US complaints that the UAE company Al Mutlaq Technology had bought $100 million in weapons from North Korea including machine guns, rifles and rockets.
"Given the inaccurate or false information we have seen in previous months regarding the process in Libya and the UN and my role, I believe it is imperative to be extremely cautious about the most recent reports," Leon said.
"This is the most critical moment for peace in Libya," he added.