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Dreamweaver CS5 is a solid, well functioning program. After all, there is a reason that Adobe is the industry leader in several web development programs.
Is it worth upgrading to? Probably not. Unless you absolutely need a feature like BrowserLabs or you're upgrading from a very old version of Adobe (or Macromedia) Dreamweaver, you could probably go without until the next version or two.
If you're someone new to HTML editing, I suggest cutting your web design teeth on a free program or other web design alternative first as this is definitely not for beginners. However, if you are part of a professional web design company and you have been using something else, or you've been using a fairly outdated version of Dreamweaver, CS5 is worth the upgrade. If you're serious about web design, Dreamweaver has no equal in the industry - it is a program that does it all.