The Argentine great could replace Cesar Farias who quit in November last year.
An imprisoned former police commissioner has gone on a hunger strike for freedom.
Ruling Socialist Party legislators voted to ask the state prosecutor to investigate Maria Corina Machado.
Official said the captain was shot late on Sunday at a street barricade set up by demonstrators.
Protesters are demanding political change and an end to high inflation and crime rates.
Activists blamed armed government supporters for shooting a student near his home in Valencia City.