If you want to prevent that number from being able to call your Samsung Galaxy S4, you can add a number to your ‘Reject List’.
To add a number to the Reject List , you just need to follow the instructions:
Go to your Samsung Galaxy S4
Open the contact page
Select number from the list
Press Menu key
Add to reject list.
Please note that in your Samsung Galaxy S4, the Reject List just can block calls from the blocked numbers which are shown with the common blue No symbol
Another method you maybe like:
You also can use Third-party apps for blocking phone calls in the Samsung Galaxy S4.
This application both blocks calls and SMS which are unwanted, and can help manage a blacklist. It is so easy and lightweight, and does not consume any of your device’s battery power.