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Try creating a new user temporarily, log in under the new user, and see if CS4 is able to launch that way.
Also, CS4 "checks in" with Adobe over the internet -- are you blocking that communication in any way (firewall, Little Snitch, /etc/hosts file entries, etc.)? If Dreamweaver is not able to "activate" with Adobe, one of the symptoms may be a crash like you're seeing -- although a more reasonable thing to expect is a warning message. Still, it's not unheard of to think that if Dreamweaver can't activate, then it can't run, and may crash instead.
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