Some 28 staff people, including Spain's embassy staff in Libya, were expected to arrive in Madrid's Torrejón de Ardoz military airbase, the ministry said in statement quoted by Spain's El Periódico newspaper.
This is the second such evacuation from Libya this week after 37 Spaniards, their Libyan family members and citizens from other European Union countries were airlifted on Tuesday.
The evacuations come amid a rapidly deteriorating security situation in the North African country in recent weeks.
Tripoli’s airport has been closed for over two weeks as violence rages in the Libyan capital.
The clashes, the most violent since a 2011 armed revolt that overthrew longtime dictator Moamer Kadhafi, started with a July 13th assault on the airport by armed groups, mainly Islamists.
The deadly fighting has spread to other cities and on Monday a huge fire erupted at an oil depot outside the Libyan capital, threatening its vital oil industry already hit by the exodus of foreign workers.
"The Spanish Government is confident that the unstable situation in Libya will soon pass and repeats its call for a ceasefire as quickly as possible," foreign minister José Manuel García-Margallo said in a statement on Thursday.
The Spanish Government would continue to support the country's new parliament and would continue to support its international allies and the United Nations to consolidate democracy and ensure the stability of the country, the minister added.