As long as your wife has never left the country since her visa expired, she should be able to adjust status.  This is assuming she has no other inadmissibility issues.  If your wife has left the country, she may be subject to a bar due to unlawful presence.  However, the bar only takes effect if the person leaves the country.  Without further information, it seems to me you can file an I-130 petition as well as an I-485 to start the process for getting her status.However, because she is currently undocumented, you may want to check with a lawyer to make sure there are no issues that might get her placed in deportation proceedings.