It's literally impossible to write a PEG with an ambiguity. So I don't know what you mean?
Not sure how that's saying anything useful though? If you write the wrong grammar with any parsing system it's also not going to work.
S := A '+' A | A '*' A
A := ...
If you do that in most PEG systems I've tried, you're just going to get the wrong result with no indication of what might have gone wrong, unless you know where to look.
EDIT: Even making it easier to annotate the parser specifications to improve error reporting would be an improvement for many parser generators. In the past I've experimented with parser generators that included a prolog-inspired "cut" like operator that stops further backtracking, and that'd take an error message to output if nothing further can be matched without backtracking. It'd prevent the parser from "escaping" out of a likely human error and end up reporting a failure to match productions much higher up. It worked fairly well, and mimics what human parser writers tends to do in recursive descent parsers - we'll often guess at the likely error based on context deep down and bail out.