Water is the foundation of hydration, but your body also relies on minerals to regulate where that water goes and maintain the balance of fluid inside and outside your cells. These minerals, known as electrolytes, also support normal nerve and muscle function.
You get electrolytes from food as well as drinks, so hydration is worth considering alongside your diet, not simply the number of glasses you drink. For many people, water and regular, balanced meals meet those needs. An electrolyte drink can provide a convenient additional source when your intake or circumstances call for it.
Plain water does hydrate you. The question is whether your overall intake of fluid and minerals suits your needs, rather than whether every glass needs something added to it.