No, you can't use this application on Skype since it's a dedicated one using the webcam to capture still images or record videos. I've looked through various website, but I didn't find anything to mention its compatibility with Skype. It's just a standalone app that uses the attached webcam to capture images and videos (with or without sounds, this depends on the type of webcam that you have installed).
Play Camera is more of a webcam manager since it also allows you to export the data to formats.
