Been working in biopharma for 13 years. They absolutely do advertise online for positions, though as you point out, many are filled/created through networking. The real question is how many biotech firms are located within driving distance of where you live in toronto? That question should have been asked before the move there. To my knowledge, I am not aware of many firms in toronto, but that may just be my ignorance.
My advice is create a complete list of all firms within driving distance. Do not limit merely to biotech. Depending on your wife's skill set, the related pharmaceutical, medical device, in vitro diagnostics, etc industries may have really good job fits for her. Government and university jobs may also be available for her skill set, though compensation may be substantially less, but will work in a pinch until that private sector job shows up. Once youve generated that list, use it to target the most desirable firms, through every route possible (netoworking, linkedin, monster, their online website job board, Biospace, etc.). Good luck!