The man, identified as Carlos Mejias Blanco, has "admitted responsibility," and faced charges of attempted homicide and illegal possession of a firearm, prosecutors said.
Authorities also had ordered the arrest of a second man, Windy Fabiani Mejias, who was present during the incident but is not believed to have been directly involved in the attack.
According to prosecutors, the incident took place after the two men had a verbal exchange with US embassy military attaches Paul Marwin and Robert Rosas at a nightclub. Mejias then drew a gun and fired several times on the Americans, injuring them.
Venezuela has the highest murder rate in South America with 54 homicides per 100,000 inhabitants. In the first quarter of 2013 alone, there were 3,400 murders, according to government statistics.
Several diplomats have been victims of attacks and kidnappings in recent months in Venezuela. In May, the wife of a Paraguayan diplomat was injured in a shooting outside her home.
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