User blog comment:WonderfulAsia/Hetalia English Dub Cast Updates/@comment-1271618-20100708215257

Ukraine did debut in volume 2 for the strips with her and Belarus. Belgium's volume debut was 3 with "Boss Spain and Chibiromano". The webcomic world meeting is technically Belgium's first appearance in the non-published strips, though if you want to count that art in the Isolation strips you can do that too.