When taking over the head position of IT Administrator, what should I ask?

I am being asked by my employer to take over the position of IT Administrator for his company as the previous IT Admin is moving on to different things. I have my degree in Network and Internet Security and as such also have a background of 4 years hands on experience in the field. I have not been the head admin for a company of this size and feel a little daunted by the task that this will put on me. If I could get a little input from my fellow peers and just see what you would ask the previous admin if you were in the same position. Thank you in advance.