Get submission values from a Webform
If I understand you correctly, you'd like to get a hold of the data before it gets inserted in the database so you can do something else with it?

If this is the case, hook_webform_submission_presave is your friend.
The $submission object will hold the submission data. This lets you change it before it's inserted in the database or, as in your case, just do something else with it.

Here's a list of all the webform hooks for D7 (with a link to D6 hooks as well if that's what you're using).