Postfix works fine when compiled and linked with OpenSSL 1.0.0. However, when migrating from OpenSSL 0.9.8 to OpenSSL 1.0.0, there is a potential (in)compatibility issue with CApath directories.
If you use a "CApath" to store root CA certificates for either the Postfix SMTP client or the Postfix SMTP server, be aware that the hash value of the issuer DN is computed differently by OpenSSL 1.0.0, and a CApath directory hashed with OpenSSL 0.9.8 utilities will not be usable by software compiled with 1.0.0 libraries. Conversely, if you use the OpenSSL 1.0.0 c_rehash (your PATH must include other OpenSSL 1.0.0 command-line tools before the corresponding 0.9.8 versions if also installed), the resulting CApath directory will not work with OpenSSL 0.9.8. If you want to be really clever, you may be able to hash two copies of the root CA directories with the same set of certificates each with a different version of c_rehash (and corresponding utilities from the appropriate OpenSSL version) and then combine the set of symbolic links into a final directory that should work with either library. If you decide to take this approach, test carefully! No warranty! -- Viktor. P.S. Morgan Stanley is looking for a New York City based, Senior Unix system/email administrator to architect and sustain our perimeter email environment. If you are interested, please drop me a note.