This is a difficult question to answer without knowing anything about your environment, applications or infrastructure. First, you will want to review the new features in Oracle 10gR2 before you upgrade. The new features guide can be found here.
Second, you will want to read through the Oracle 10gR2 upgrade guide. This will provide you with an idea of what you need to test in an upgrade. The upgrade guide can be found here.
My advice would be to thoroughly test the upgrade process in a non-production environment several times before attempting it in production. After each database upgrade, I would ask the application support teams to functionally test any applications the database supports. This way, you will be able to pinpoint any performance or code changes as a result of the upgrade.
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