Well, fortunately Hwy 69 is much better than it was say, 20 or 30 years ago! You could try the road out to 'Go Home, ON' but it's been a ghost town for a long time and I don't know what the road is like anymore. That's a long stretch of road, and a LOT of beautiful scenery. The leaves will be done by then, but the country still has its own charm. Just in provincial parks you could start with Killbear, Sturgeon Falls, Grundy and French River, and that's before you even get to Sudbury. Speaking of parks, be aware that October is moose hunting season. As someone who has worked in the field a lot over the years, I've met the full gamut from experienced woodsmen to trigger-happy drunks, and unfortunately many of both and a lot in between will be in the woods around then. Best to 'focus' on woods that are protected, like parks unless you enjoy the thought of being shot at.
Parry Sound itself used to be an important shipping port, and if you wander down toward the water you might still be able to find some of the old industrial neighbourhood. It's been too long since I used to travel that part of the world for me to give you any real information on what things are like now.
Have fun with it!
Mike. P.S. Contrary to popular opinion it's WāWā, not WăWă (hard 'a' sound - the Anishnaabek word for Canada Goose)