No, it would not behoove us to work with Libertarians* (or minarchists, etc) any more than it might behoove us to work with any other statists. Which means maybe, at times, in certain cases and on certain projects, sure, it would make sense to work with certain libertarians, but not across the board, and not because they are striving for a smaller government, because generally that isn't all they are striving for.
Most Libertarians that I've encountered are rabidly pro-US and pro-capitalism, many right-libertarians (including Ron Paul) are both religious fundamentalists and quite reactionary as far as their actual views on individual liberty (see for example, Ron Paul's opinions on abortion) which places them firmly outside of the realm of allies to any anarchists that I am friends with.
*I'm capitalizing Libertarian to imply statist, pro-capitalist libertarians, since the term is older than that and in many places and at many times is synonynous with anarchist. I would actually argue that the Libertarian Party-types are actually misusing the word.