The Spanish words 'año' (year) and 'España' (Spain) contain the letter ñ, called eñe.

It comes from a double nn.

One of the n's was abbreviated as a squiggle on top of the other: ñ.

'Año' comes from Latin 'annum' with nn, but 'España' comes from 'Hispāniam'. My graphic explains how it got its ñ:
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