Yes, but in terms of convenience, AC leaves LIM at 2:15 AM or something like that, getting into YYZ at 11 AM. Also, AC only flies this route 3 times a week, I took YYZ-EWR-LIM on CO and found it to be quite good. It's a day flight EWR-LIM and the return is a night flight. Personally, I prefer day flights as I like to read on the plane and can't sleep well on a night flight. On my return flight I was seated with two people from Vancouver who were flying through EWR to Seattle.

Try searching orbitz for the best fare/ schedule combo, in addition to LAN maybe CO through IAH or DL through ATL or AA through MIA.