Make sure the person you're calling has the latest version of Skype.
"With Skype and Alexa, you can now connect with your friends and family around the world completely hands-free". On the Echo Show, you'll be able to make video calls as well. You could already make calls between Alexa devices, including phones with the Alexa app. You can use that credit to make global calls or reach people who aren't on Skype. if you're opposed to using Alexa's built-in calling feature that does it for free.
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Here are a few of the example commands from the Skype-Alexa website: "Alexa, Skype Mom; Alexa, call Dad on Skype; Alexa, pick up". Other countries will get it soon. At last count, Skype had around 300 million monthly active users - a fairly substantial number.
To incentivize linking your account, Microsoft is offering users 100 free minutes a month for two months after linking your account.