Ambiguity means different things to CF and PE grammars. For CF it is obvious: two derivations are possible for a given string (or prefix, depending on your flavor).
But for a PE grammar, it's harder to define. It's not "an ambiguity in the equivalent CF grammar" because what does equivalent mean ? Same derivations ? Then it's not ambiguous, because PEG only allows single derivations. Same rules ? It's obvious that you can't treat a PE grammar as if it were CF and still expect it to work.
I believe the actual problem isn't ambiguity, but rather brittleness. What transformations can be applied to a grammar while keeping the same meaning ? In other words, how easily can it be refactored ?
Consider this small grammar:
STATEMENT -> DEF | EXPR | VARDEF
DEF -> ('int' | 'bool') ID ('=' EXPR)?
VARDEF -> 'var' ID '=' EXPR
In a context-free grammar, you have mathematical proof that you can convert the above to this cleaner version without altering the meaning:
STATEMENT -> DEF | DECL | EXPR
DECL -> ('int' | 'bool') ID
DEF -> ('int' | 'bool' | 'var') ID '=' EXPR
In a parsing expression grammar, this conversion might change the meaning, depending on what EXPR can recognize.
Personally, I'd rather deal with shift/reduce conflicts than try to determine, by hand, whether a minor refactoring of my grammar will cause some obscure edge case to be parsed differently.