There is some history in Java using @ initially as a marker in Javadoc comments  and later in Java 1.5 for annotations , 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.
The decorator pattern, also known as the wrapper pattern, is when you wrap an object within another object, thus providing a means of enhancing or overriding certain behavior. The wrapper object will delegate any incoming method calls to the original object, unless it defines a new method to enhance or replace the original object’s behavior. By using the decorator pattern, you can dynamically create as many decorated objects as you want, each enhancing the behavior of the original object in a unique way — and all without mutating the original object. In this manner, you can effectively add, remove, or extend behaviors at runtime.
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... the keyword starting the line that heads a block draws a lot of attention to it. This is true for "if", "while", "for", "try", "def" and "class". But the "using" keyword (or any other keyword in its place) doesn't deserve that attention; the emphasis should be on the decorator or decorators inside the suite, since those are the important modifiers to the function definition that follows. ...
There have been a number of objections raised to this location -- the primary one is that it's the first real Python case where a line of code has an effect on a following line. The syntax available in 2.4a3 requires one decorator per line (in a2, multiple decorators could be specified on the same line), and the final decision for 2.4 final stayed one decorator per line.