How do I print curly-brace characters in a string while using .format?

You need to double the {{ and }}:

>>> x = " {{ Hello }} {0} "
>>> print(x.format(42))
' { Hello } 42 '

Here’s the relevant part of the Python documentation for format string syntax:

Format strings contain “replacement fields” surrounded by curly braces {}. Anything that is not contained in braces is considered literal text, which is copied unchanged to the output. If you need to include a brace character in the literal text, it can be escaped by doubling: {{ and }}.