As I remember the governor accepted their services. They were later disbanded and never called into the Confederate Army itself, but I've read somewhere that they were called up again to help defend New Orleans when the Feds came. Unfortunately, I don't think they made much of a defense of New Orleans at all.
Their main service across the state was to provide local safety and order during the first year or so of the war when many of the local white men were off at war. They were a home guard. How long they continued to be so so outside of the area controlled by Federals, I do not know.
I'd check it, but I'm not sure what old Louisiana newspapers my local library has outside of the Picayune, which published under the eyes of people like Beast Butler after the Feds took New Orleans.
There was a mass resignation of the Federal Native Guards when they were given the choice of returning to their plantations or staying in the Federal army.
Everything I've read indicates that they banded together as private citizens and offered themselves in service to the confederate military and their offer was turned down flat. In fact many later joined the Union army.