The exact behavior here depends entirely on the JVM implementation. In spec (that is what a proper JVM implementation needs to provide you), it can happen in parallel, it can happen first before your code executes, or it can not happen at all.
In practice, my observation on JVMs I have happened to observe is that it runs immediately in a separate thread. However, in some cases multiple calls spawn multiple threads, sometimes it queues the requests on one thread. The Garbage collection launched was always a "stop-the-world" type (that is it was very complete and slowed or paused the application).
However, given your comment to @Chris Dail, your underlying problem isn't the behavior of a System.gc() call. Calling System.gc() can have some uses. It can be used clear memory so you can get a sense of how large the footprint of the application actually is currently. It can also be used as a strategy to ensure that a stop-the-world garbage collection happens earlier so that it "stops the world" for a shorter amount of time because there is less memory to clear. (I should note that as JVM's get more and more sophisticated this kind of thing is less and less necessary, and actually becomes counter-productive).
What it does not do however, is in any way solve an OutOfMemoryError. The JVM will not give you an OutOfMemoryError until it has garbage collected to the best of its ability. Calling System.gc does not change that. If you have an OutOfMemoryError it is likely because you are holding reference to objects in ways that you don't really need, but that are preventing those Objects memory from being reclaimed.