The only way I know is to call customer service at 1-888-294-6804 and ask them to block it for you.
Minniehaha is correct, if you have prepaid you will need to call customer service to request call blocking. The directions below that I provided are for Post-Paid.
Verizon Wireless offers a call-blocking feature that is included with your calling plan called Call and Message Blocking. This feature allows customers to block up to five ten-digit numbers (per wireless number on the account) from calling or messaging them. Call and Message Blocking does not block calls from unknown or restricted numbers or messages sent from an e-mail address. The block will remain active for 90 days. Once it expires you will need to request to have the block reinstated.
Call and Message Blocking can be added/removed online by signing in to my Verizon Verizo https://login.verizonwireless.com/amserver/UI/Login using your Account Owner user ID and password and doing the following:
1. Click on “Block Calls & Messages” icon located under “Plan” in the “I Want To” section at the bottom of your home page.
2. Click on the “Call and Message Blocking” tab (next to Parental Controls.)
3. Enter up to five 10-digit numbers under the Call and Message Block tab and click "Apply" once completed.
If you are on the daily prepaid Blocking is not available you would have to call customer service. If you are on the Monthly plan you may beable to Block using the direction given by the service Rep.
How do I talk to an actual person?
Kelley do mean a C.S.R to do that you can call *611 from your phone or from a Land line the No. is 1-800-922-0204 an listen to the Promps an then Enter your phone info When they ask. Usually i just wait till it says No.2 for Technical Support then it ask what i want to do i just say Representative an if ask a again i say Rep again till it take me to one After that explain what you want done That should Do it. Good Luck. B33
P.S. if your wanting to get this done Tonight i would get on the phone rather Quickly as they close in about a Hour.!