There is some history in Java using @ initially as a marker in Javadoc comments [24] and later in Java 1.5 for annotations [10], which are similar to Python decorators. The fact that @ was previously unused as a token in Python also means it's clear there is no possibility of such code being parsed by an earlier version of Python, leading to possibly subtle semantic bugs. It also means that ambiguity of what is a decorator and what isn't is removed. That said, @ is still a fairly arbitrary choice. Some have suggested using | instead.
Syntactic constraints. Python is a syntactically simple language with fairly strong constraints on what can and can't be done without "messing things up" (both visually and with regards to the language parser). There's no obvious way to structure this information so that people new to the concept will think, "Oh yeah, I know what you're doing." The best that seems possible is to keep new users from creating a wildly incorrect mental model of what the syntax means.
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