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Take bus 411 express (or 211 non-express) from Lionel Groulx subway station. From the terminus, continue walking westward (or take bus 251). Turn right on Saint Pierre St and head straight. Going to Toronto, you can hitch at the on-ramp of Highway 20, after the underpass or walk the bridge and hitch directly on the road as it becomes a boulevard and there is plenty of space for vehicles to stop after the intersection, near the tourist information.
Another possibility is to get off at Vendome metro station and take the bus 90 going west (ouest in French). Going along St Jacques street, at the fork of the road you will see a gas-station and a McDonalds - the bus will go left, and you should get off and go right - which is where cars going west will pass. This is still fairly in the city but if you hitchhike with a sign saying you want to go west on the highway 20, you should get a ride quite easily. It is advised to go there early and try to catch the people going from Mtl to To.
Google Maps: [https://www.google.ca/maps/place/McDonald's/@45.4535913,-73.6338266,15z/data=!4m2!3m1!1s0x4cc910d32ed67863:0x2b15bbb5fa300073 hitching spot]
If you want to go to Ottawa, there's a great spot right before highway 40. Just continue straight past the 20 and along 'Avenue des Anciens Combattants' for about 10 minutes. For pictures of the spot, see: http://imgur.com/v2vDG and http://imgur.com/wPYQK