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Its very easy to add people to your Skype contacts list. You however cannot add contacts from the skype website interface. You can only do it from the app. You can add a single contact, or import multiple contacts
Launch the Desktop app and sign in to skype.
How to add a Skype contact:
You can search for the skype contact you want to add either with the full name, username(skype name) or email address. If there’s one match in the search results, and it’s the person you’re looking for, click their name or profile picture. The skype name is the most accurate since its unique.
If there’s one match in the search results, and it’s the person you’re looking for, click their name or profile picture.
Click Add to Contacts and enter some text to introduce yourself and click send. When your new contact accepts your request, you can see when they are online instead of a question mark.
How to Add a Phone contact to skype
Click the call phones icon
Select a country from the flag menu drop-down list, then type in your contact’s phone number.
click Add to Contacts. Enter the contact’s name and select the phone type from the menu – Mobile, Home, Office or Other. Then click Save.
Ofcourse You’ll need a little Skype Credit or a subscription to call mobiles or landlines.
You can also import your Facebook contacts into skype using the desktop app.
In the menu bar, click Contacts then Import Contacts…
Enter your user name and password for your Facebook account and click Import.
The people in your Facebook address book who already have Skype accounts or phone numbers associated with their Facebook accounts are listed.
Uncheck those you don’t want to import and click Add contacts.
Your selected contacts are added to your contact list, but will appear offline until they accept your request.