A lot of people do use MongoDB for a low-medium grade cache and it works just great.
Because it offers more functionality than a simple key value store via ad-hoc queryability it isn't as pure of a caching layer as a memcache or redis (it can be slower to insert and retrieve data).
Extremely high performance is attainable (the working set is in RAM after all), but the data model is heavier.
However, on the flip side, MongoDB does offer a persistance layer that makes a lot more sense (to most developers) for the type of data that is most likely needed at a later time, unlike Redis.