Unfortunately, you can’t talk over Skype while you’re playing a game. To make a call, you have to pause the game. You can return to your game when the call has finished.
After you launch Skype, you can press the PS button to minimize Skype. If somebody calls you, an alert message appears in the upper right corner of the screen to notify you of the incoming call and the caller (if available). If you’re playing a game at that time, you can press the PS button to stop the game and a message will appear asking if you want to accept the call. When you click Accept Call, Skype will launch, and the call will start in audio mode only. To use video, you need to turn your web camera on. After the call, you can minimize Skype and continue your game from where you left off.
Important: While playing some games, WiFi and 3G/4G are turned off to maximize CPU (central processing unit) and memory resources, and also to minimize power usage. In these cases, Skype will go offline.