Yes, you can make voice and video calls using the PC version of LINE.
You can enjoy voice or video calls with any of your LINE friends, as long as you are on each other's friends lists.
There are 3 ways to make voice or video calls:
Calling From Your Friends List
Click Friends to bring up your friends list, then right-click on the friend you wish to call. Click either Free Call or Video Call to start a call. Your call will begin once your friend accepts the call.
Calling From a Chat
Click Chats to bring up the list of chats and open the chat of the friend you wish to call. Click on the Free Call or Video Call icon to start a call. Your call will begin once your friend accepts the call.
Calling from a Group Chat
Open the group chat and click on the number icon at the top of the screen. Click the profile picture of the friend you want to start a call with and click Free Call or Video Call to start calling. Your call will begin once your friend accepts the call.