Yes, acetate buffer can be used as electrolyte. I use 0.1 M acetate buffer without issues.
You have to bear in mind that acetate ions are bigger than for example Na+ or K+, so the ionic conduction won't be as good as using those smaller ions.
You can use any buffer as an supporting electrolyte for electrochemical measurements , it deepends on your experimental purposes (acetate - for acidic solutions, phospahte - for neutral solutions, ammonia buffer - for basic solutions, etc),