Instead of hitchhiking you might consider signing up for a carpooling or ride-sharing service. My ex used to work in a city about seven hours outside of Montreal on the weekends and would carpool with people he met through a ride-share service all the time. Some people giving rides were sketchy , though, but most were not. The safety benefit is that you can email friends and family the info of who you are going with before you leave. I can't remember the name of the service that he used, however. But I am sure if you google it, something will come up. Might be an idea?
Try the various craigslists in Canada. There are always people posting rides offered. Always check the destination and departure areas as people don't post in both (e.g., they may offer Montreal to Toronto and post it in Toronto if they live there but not in Montreal where the ride originates).
Programs: AA, UA, US, DL, HHonors, Hyatt, Club Carlson, IHG
The carpool/rideshare option is useful as I used it before in the US. You can actually meet first before deciding to travel together.
Hitching is not that bad. You just have to be careful and use some common sense. It sounds racist but it seems that a White male is more likely to fit the highest risk profile. On the other hand, the elderly or overweight minorities are less likely to be psychos. What do you think?