Unless the BIG takes an entirely different stance on it's members academic's then WVU will never be a member of that conference, though they would bring some interesting matchups, same with the SEC (east).
WVU's best fit is the ACC and the ACC should want them too imo. They claimed that they passed on WVU over academics when the BigEast folded but then after the BIG took Maryland from them and WVU was locked into the Big12 and no longer an option they took Louisville who's academics were nearly the same so, jmo I think they have a real shot at being in the ACC when (not IF because schools ARE going to leave, the money gap is going to force that) they start losing schools again.
Now I'm not saying your gonna put WVU vs.________ on Saturday afternoon/evening and beat the ratings/views of what the SEC and BIG are going to be putting in those slots but you put em on say, Thursday night or Saturday noon ect. and have the Backyard brawl v Pitt, the Schwartzwalder trophy game vs Syracuse, The Black Diamond trophy game vs VT , WVU vs Louisville (market as Hatfield & McCoy's game) plus new regional games that could easily develop into good rivalry/trophy games vs UVA, Wake, and I'm sure any of the other NC schools due to so many WV transplants living in NC and I think the ACC could get some better interest/ratings than some of the current ones.