The short answer - it depends.
Majority of MVStore operations for in-memory case are non-blocking, especially if you use it in a low-contention scenario, but if you have many threads competing for doing some map updates, threads may yield, sleep or even go for lock acquisition after some failed non-blocking attempts. Your read operations are guaranteed to go non-blocking in any case.
Just curious, what you are trying to achieve with pure in-memory MVStore (without transactional functionality), that can not be done with stock JDK SortedMap implementations like TreeMap or ConcurrentSkipListMap?