It says that on the
wikipage, but if you go to the direct source, it’s different. The translation is noted to be rough, but the distinction is nonetheless made very clear [x].
Netherlands and Belgium are the ones that are
siblings.
Luxembourg refers to
France, Spain, Netherlands, and Belgium as big brother and sister respectively
as terms of endearment.

This is a common trope in
the series, although it often causes a lot of confusion because it’s taken
literally.
It doesn’t help that the
trio was once referred to as sworn siblings. [x]
Although, if you go on
the above piece of information, it seems to be conveying a bond similar to siblings. It’s not uncommon
for close friends to consider themselves siblings – in this case, it would be
Luxembourg due to his close proximity.

Just to give more
examples of this trope, France is referred to as a big brother type/ big
brother of the world.


Hungary is referred to
as an older sister.


And so is Belgium.

I’m working on a larger
post that will go into more detail about the brother/sister figures and relations,
but it’s going to take some time.