Yes there are substitutes in volleyball but a coach/team can only have so many subsitutions. There can only be 10 subsitutions per game and an overall 30 substitutions for a match of 2 out of 3 games or an overall of 50 substitutions for a match of 3 out of 5 games.
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If you mean how do players substitutes in volleyball, they do a motion with their arms/hands, then the down ref will let them go after they have touched hands. If you mean how many substitutes are there, there are twelve subs per a set in a volleyball match.