I suspect the lack of response is because folks aren't quite sure what you're asking about. The best I can guess is that you want to save a copy of an app from your phone onto your computer. I don't think Kies can do that.
There are many ways to do it. Being rooted helps. You could use a file manager like ES File Explorer to copy the .apk file from /data/app to the SD card. Speaking of ES File Explorer, you could use its app manager function to make a backup copy on the SD. Once it's on the SD card you could proceed to use Kies or any other method to get it from there.
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