Having worked on a particular navion for the last 1.5 years, my advice would be to have a through pre-buy inspection. Look over the hydraulic system, make sure everything is working in the "power pack" (valve unit behind panel). Ideally, jack the plane and check the play in all the landing gear linkages. Check out the tail section, specifically where the horizontal stabilizer attaches - there are a few nasty AD's on that part. Also look at the aft bulkhead where the tailskid connects. They are almost always cracked. If the airplane has the original windows held in with the rubber molding, be advised that it is no longer available, and you'll have to get updated windows at some point.
Get someone that really knows Navions to look at it!
If everything looks good, they can be a really nice plane. However, they can also turn into a money pit, more-so than other light aircraft.
From a flight standpoint, I enjoy flying the navion, and find it has a very solid feel to it. Not exceptionally fast, but fun to fly nonetheless.