Busquets' positive outcome has thrown Spain's tournament preparations into chaos with all the remaining 23 players moving into isolation together with the coaching team.
An Under-21 side headed by their trainer Luis de la Fuente will face Lithuania on Tuesday in what was likely to be the nation's final warm-up match ahead of the Euros.
Coach Luis Enrique called up a set of six players, such as Chelsea goalkeeper Kepa Arrizabalaga, to match the squad. They will train separately in"parallel bubble" away from the main Euros squad with a view to them being inserted if the need occur.
So far, all the other players and staff have tested negative.
"We're creating an exception only because they represent us at a top level competition," Rodriguez Uribes told Cadena Ser radio station, adding that they were already planning to provide them the shots prior to Spain's captain had tested positive.
Unlike other nations that have opened up vaccines to all adults, Spain is slowly working its way through age groups and is now focusing on individuals aged 50-59, with some areas making a start on 40-49 year olds. More than 23% of Spanish population are already completely vaccinated.
Rodriguez Uribes said which vaccine the football players could get hasn't yet been decided yet, therefore it is not clear when they would have immunization.