It is different to say that a person is tired of work rather than to say he is tired from working. A person who is tired of work doesn't want to work anymore. But a person who is tired from working is physically exhausted. A person might say, for example:
I have been working all day, and I need to rest. I am going to stay home for a while.
I have been working, and I need to rest. Give me some time, and maybe I'll join you later.
I am tired from working. I am going to stay home and rest. Could you bring me some takeout?
I've been working a lot, and I'm tired. I'm going to take a nap. But you go out and have fun.