VR won't work with the steam link and if it did the latency would be too slow to be comfortable.
A lot of people ask this question and give this response, but it's not the whole story.
It confuses a lot of people but the Steam Link is advertised as "working with the Vive" because it lets you mirror the game being played to your TV.
If like most people you have the Steam Link in another room for your PC (i.e. the purpose of the device in the first place) this likely isn't that great a feature because you can't see what the person is doing in the real world - which can be half the fun.
However, it does give you a wireless (or network based) way to extend what is being shown on your monitor to something like a projector so you could see what your friend is playing on a bigger screen.
In the real world I've yet to find anyone actually making use of this feature in a meaningful way as if you've got your computer in the same room as your bigger screen most people will have it hooked up with an HDMI cable already.
P.S. On topic, having both, I find it next to impossible to recommend one other the other.
Subjectively the Rift has the better screen, controllers and headset comfort.
The Vive has the better tracking solution that works better with larger rooms without extra cost (i.e. 3rd sensor for the Rift)
Ignore the fact the Vive has a camera, I've even disabled mine, it's just not that massively useful in its current state.
However, I'd say the Vive is the most robust solution out the box as it's least likely to cause you issues with USB compatibility/overloading and the tracking solution is easier to setup/more flexible.