The correct option is A Although he is very rich and famous, he is very humble.
Option B is incorrect as it uses 'of' after 'despite', which is redundant here. Despite means the same as 'in spite of'.
Option A is the correct choice. Although/though are subordinating conjunctions used to connect a subordinate clause to the main clause. It can be used to start a sentence. If you start a sentence with an "although idea", end it with a comma, and follow it with a real sentence as done in option A.
Option C fails to pick the sense of the individual sentences, which present richness and fame in a negative sense.