It depends if you want to pay for it/hold valid licenses for business use or not ? As I understand WINE is a public license and VMWare is commercially licensed.
On a technical front I've played with both, sorry, done extensive evaluation work on both, and prefered VMWare. Not really any major reasons, except that I could install as many different OSs as I wanted, not just Windoze. We ended up with LINUX on M$ on LINUX with a further nest of Solaris on LINUX. Of course there is an overhead, but isn't there always.
On the other hand I'm pretty sure that WINE is a more 'efficient' way to do this kind of OS nesting and of course free is the cheapest that you can get. Ian
"IF" is not a word it's a way of life