Go for it, my engine block ground is to an alt bolt, but then I've got a ground from the alt to my strut tower and another from the batt to factory chassis location.
The point of grounding the engine block is to ground the alternator chassis, it's just some engines have the alternators at hard to reach points and the engine block has a lot of easily accessible bolts.
That's what it's designed for. Quite a few brackets actually have a '-' or 'NEG' written on one of these bolts. It is grounded to the alt, the generating source of your current. What better place to have a solid ground?