Yes, it worked finally, but not as you described. I had both ethernet and wifi turned On and one interface had direct access to the internet, therefore, was bypassing the PfBlockerNG.
Now I ran into another problem. :)
Everything is working fine, except that one PC is able to bypass PFBlocker. I do not know how but I checked directly and also did Nslookup but it's getting through. All the other workstations are getting blocked except one.
This is the firewall rule screenshot
25521629-221e-4d17-b6ee-be1d8464bb60-image.png
Screenshot of NGAlert showing blocked site access from other PC
ed30728e-3c6c-46d1-955d-5b63e2112f57-image.png
Nslookup screenshot from the rouge PC
8419eb6f-0874-4572-99a7-be567b06a391-image.png
From the other PC it shows 10.10.10.1. So its getting blocked there