Yes, it will work.
I do mean the starter program with which can control the robot with IR remote controller as well as other program in the mBot 101 library.
If you know arduino program very well, you may be able to reprogram for the robot (switched with new board) to achieve the same function.
You can program the robot (with new board) with mBlock software, but the graphical program may not perform as good as the example arduino programs in the library. Anyway, you can try it to challenge yourself.