According to Viber, if they know your number you can't block them.
"Viber uses your contact list to recognize other Viber users. Viber works like a regular phone so no one can call you on Viber unless they already have you listed or know your telephone number. Since the person calling you has your number, there is no way to block him from calling you, not via Viber nor via your regular carrier. When you decline a call, the caller will be unaware, they will still hear ringing until they hang up or until the call attempt times out (approx. 50-60 seconds). You will then receive a missed call notification."
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