Both are prescribed for spasticity in MS. I've only been on baclofen, but my understanding is that Zanaflex would work quicker and short term where Baclofen would work in the system gradually and hope to provide more long term effects.
I can't speak to the difference in the mechanism by which they work but this is my general understanding.
When I was prescribed it I wanted something that I could pop and have it work, but the doc said he wanted to get out ahead of the problem, and started me on the baclofen.
I just started the zanaflex, and so far seems to help. It takes the problem away slowly but at least I am not all stiff and unable to move. I normally take it at night due to the fact that it can make you tired, but I have had to take it during the day and did not make me any more tired than I already am.
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