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According to this wikipedia article it does.

However a chef at my restaurant had not heard of this.

The wikipedia article seems to be missing citations, and I don't have time to perform an experiment.

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up vote 10 down vote accepted

You have misread the Wikipedia quote. It says (emphasis added):

Kale freezes well and actually tastes sweeter and more flavourful after being exposed to a frost.

While not terribly well written (since there is the red herring that it freezes well), this doesn't mean that the harvested plant was frozen, but rather that the live plant in the ground was exposed to frost. This causes it to begin converting starches to sugars in preparation for winter, giving it a sweeter taste.

Per Burpee, for example:

Frost enhances the flavor. Some of the tastiest kale is harvested under a foot of snow! Never harvest kale until after a hard frost or two. A few freezing nights make all the difference in flavor as the kale plants need a hard frost to transform their starches into natural sugars.

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but are you sure that this transformation cannot happen after harvesting? It happens when refrigerating harvested potatoes IIRC, so why not in kale? – rumtscho Dec 19 '13 at 23:09
@rumtscho I am not 100% certain not being a biologist, but normally if a vegetable is frozen after harvesting, it is left that way, and that would essentially shut down its metabolic processes. So I think this is a true inference in practice, even if there is some theoretical possibility the kale is harvested, frozen, thawed, and still not senescent and so continues starch to sugar conversion. – SAJ14SAJ Dec 19 '13 at 23:10
Parsnips are also sweeter after a frost, and I have picked, frozen, then used them to get the same effect – Kate Gregory Dec 20 '13 at 18:31

I found this online. Doesn't say anything about freezing, but frost does it too. So, I would think frost makes it sweeter.

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