Dehydration is a real danger in heat, hard exertion, and especially during illness with vomiting or diarrhoea — where it can become serious quickly, particularly in children and older people. Plain water doesn't replace the lost salts your body needs to actually hold onto that water. Rehydration salts restore the electrolyte balance, so you recover far faster and feel human again sooner.
They're light, keep for ages, and address a genuine medical need that water alone can't. A few sachets in a first-aid or travel kit is cheap insurance against the flattening effects of a stomach bug or a scorching day's exertion.