My wife just bought a higher mileage (83k) '13 S4. The B8.5 should be fairly reliable, especially for an Audi.
Make sure the DSG service has been done, ever time, on time. If not, walk away. Waterpump should be fine now. PCV and thermostat can be an issue but not a guarantee. If replacing one, replace both as they both require pulling the supercharger. Otherwise everything else seemed to be pretty trustworthy on these cars. Obviously a good service history is a big plus - my wife's car had very extensive records, so I could really tell it was cared for during its lifetime (plus its condition was much better than average for its age and still smells new).
The wife and I like buying the German cars after they tank in value after a few years and some miles. I turn my own wrenches and we have 3 vehicles between the two of us, so a little vehicle downtime isn't a big deal and allows me to buy parts online at a significant savings. That said, I've had very little downtime with our couple of German cars. Wife has had her B7 A4 for 10 years and it has been pretty reliable with a thermostat and diverter valve being the main failures (and now a dying torque converter - common on the B7 and I will be selling it like that). I have a E92 335i, which is notorious for being unreliable. Only major issue was a waterpump - otherwise minor stuff to replace.
All owners should get a VAG-COM. $200. Not only for coding features aspect, but for reading/clearing fault codes. For instance, my wife's S4 had a adaptive headlight failure (must get a Prestige model to get this feature). Ended up just being a blow H7 bulb. No biggie, could happen in any car at pretty much any mileage. The problem is that without the VAG-COM, there is no way to reset the code and have the lights work after replacing the bulb. For my BMW, I have all the coding stuff as well (cheaper but harder to use). It has been necessary as well as I've had to replace a couple of modules and that can't be done without the software.
This is where the dealers make an unnecessary killing with the ability to code and reset stuff. I had the Footwell module fail on my BMW. Easy to find online, fairly cheap when purchased used. About a 15 minute job to swap - I would have wasted way more time going to a dealer than DIY. The problem is without the coding tools, you can't code the new VIN and flash the correct vehicle order to the unit, so it wouldn't work. Dealers make it out to be some big deal but it is actually very easy to DIY once you learn the basics. From my 10 minutes of playing with VAG-COM, it should be 10x easier than the BMW tools.
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