I do this.
I have the Calibre library on a portable drive and I just point calibre to the library folder on the drive. The only thing you have to make sure of is to ensure that the drive letter is the same every time otherwise the library links wont work. I've been doing this for over a year and have had no issues at all.
I did go one step further and am using the portable version of Calibre on the same drive so I don't actually have it on my laptop at all. I do however keep a copy of my library backed up on to my Desktop as a "Just in Case" as I have invested a lot of time in getting it the way I like it.
Hope this answeres your query
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