This would be in the binding configuration section of the service host's .config file. Depending on the binding being used, you can set things like maxConcurrentCalls and maxConcurrentSessions, there are usually default limits for them imposed by WCF.
Real life example:
<system.serviceModel>
<behaviors>
<serviceBehaviors>
<behavior name="ServiceBehaviorBasicHttp">
<serviceThrottling maxConcurrentCalls="1000" maxConcurrentSessions="1000" maxConcurrentInstances="1000"/>
<serviceMetadata />
</behavior>
</system.serviceModel>
Or in code behind, something like this:
ServiceHost host = new ServiceHost(typeof(MyService));
ServiceThrottlingBehavior throttleBehavior = new ServiceThrottlingBehavior
{
MaxConcurrentCalls = 40,
MaxConcurrentInstances = 20,
MaxConcurrentSessions = 20,
};
host.Description.Behaviors.Add(throttleBehavior);
host.Open();
Taken from here: WCF: How do I add a ServiceThrottlingBehavior to a WCF Service?