Programmatically get webform submitted field values
In recent 3.x and 4.x versions of webform it has an hook based API to allow you do stuff with submitted webform values.

Look at like hook_webform_submission_insert() or hook_webform_submission_update() (if your webform has Drafts enabled for instance the final submission is an UPDATE call with isNew == False and isDraft == False).

The functions take a parameter $submission that is a PHP array of the submitted form values ... You can do whatever you want with them from there.