When a native English speaker hears the first sentence, he mentally supplies a missing verb to go with "to him", so it is as if the sentence were actually:
[It seemed] to him that the hectic work was both fun and rewarding.
The comma empasizes that this is what is going on because it clearly separates "to him" from "fun and rewarding".
In the second sentence, "for" works much better. You could use "to" and write "fun and rewarding to him" but if you did that the phrase would again belong with a verb - "was" in this case - rather that with "fun and rewarding". Thus the sentence would be the same as
"The hectic work was, to him, both fun and rewarding.