If you load the French league(or just France as an additional nation) and Guadeloupe you are able to take control of that country, it is not a full Fifa member, but there no fun in managing that country either as you are not listed on the Fifa world ranking list. They have an agreement with the CONCACAF, however, since there is no Carribean nations cup (not to be mistaken with the Gold Cup) I dont know if you are able to participate in the Gold Cup. I know that Zimbabwe is available, as is Albania, but I don't think that Afghanistan is. Other non Fifa members that are available are: French Guiana, Martinique, (perhaps) Reunion. Thats it
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