Since I have a book on all independant countries I've managed to make a list on countries who haven't appeared in offical Hetalia media or don't have an canon design at all. If I've missed out any countries please mention! Also please tell me if any of the countries mentioned have appeared in offical media or have an offical design so I can correct the list.
*Republic of Ireland
*These guys have been mentioned in offical media as being relatives of England, but they don't have offical designs.
Luxemborg (has been mentioned as a relative to The Netherlands and Belgium but doesn't have an offical design)
Vatican City (hasn't had an appearence in media or an offical design unless you think Chibitalia represented this)
Bosnia and Herzegovina
* Designs have been planned for these two, Slovakia being an older brother to Czech (who would've been a female character). The countries making Czechslovakia. However I think this is just an idea and nothing offical, yet.
Cyprus (Cyprus IS NOT TRNC (Turkish Republic of Northern Cyprus) they are two different countries, Cyprus being the recognized part. Cyprus has appeared as a male character in the bonus track The Flag of Cyprus on Hetalia: The CD however he doesn't have a canon design)
Iran (Iran could also be Persia, unless you want to count them as being two seperate countries)
*Well I watched a film about The Ten Commandments and when Moses was leading the Hebrews (or Jews) back to their homeland from Egypt he referred to their homeland as Israel. And I was confused terribly by this because I think at that time Israel was called Palestine. My teachers tell me that the country has only recently (sometime last century during the 50s or 60s, can't remember) been named Israel. My dad tells me that the Jews had always referred to the land as Israel, even when the country's population consisted mainly of Muslims. Israel being the country's name to the Jews and Palestine being it's name to the Muslims. So like Iran and Persia, you can either portray the modern country as have been it's old country name or have the two countries be two seperate characters. This is long O_O
United Arab Emirates
Cape Verde Islands
Cote d'ivoire (Ivory Coast)
Central African Republic
Sao Tome and Principe
Democratic Republic of the Congo (Zaire)
*I think these guys have offical designs, please correct me in the comments if I'm wrong. Politely please!
Papua New Guinea
New Zealand (I think this country has an offical design, just no offical appearence in offical Hetalia media yet)
Federated States of Micronesia
Mexico (has been mentioned in a drama CD but didn't make an appearence neither does the country have an offical design, so right now its a non-Hetalia country)
Antigua and Barbuda
St. Vincent and the Grenadines
Trinidad and Tobago
I know micronations aren't really recognized as independant countries but this list was for fun!
British West Florida
Coral Sea Islands
Global Country of World Peace
Hajducka Republika Mijata Tomica
Republic of Jamtland
Kingdom of Lovely
Neue Slowenische Kunst
Northern Forest Archipelago
Other World Kingdom
Please note me if any of these countries have had any offical appearences or an offical design so I can alter this list (same for spelling mistakes)! I got the list of micronations from Wikipedia. Hope you like!