Anthropologic evidence suggests that many ancient cultures practiced regular oral hygiene. In fact, researchers have found recipes for teeth-cleaning and breath-freshening preparations that date to ancient Egyptian, Chinese, Greek, and Roman cultures. The ingredients have included materials such as charcoal, fruit and dried flowers, but there's no credible evidence about effectiveness of these products.
Oral care products as we know them first appeared on the scene when toothpaste was developed in the 1800s. Mouthwash was first mass-produced commercially in the flate 1800s. Most of the early brands of mouthwash contained alcohol which was used to stabilize the mouthwash formula, but today you can find alternative products that are able to provide germ-killing properties without needing alcohol stabilitization, including CPC (cetylpyridinium chloride). CPC is found in many health care products and its germ fighting ability depends upon the formula, with some products being effective for killing germs that cause both plaque and gingivitis. For example, CPC is used in Crest's Pro-Health Rinse.
Today, you can also find mouthwashes for special needs, such as sensitive mouths or braces, and for those who prefer natural products. In fact, the variety of mouthwashes and rinses available has increased dramatically in the past few decades. But the scientific evidence for their effectiveness remains limited to improving breath and preventing plaque buildup.
It's essential to remember that no mouthwash is a replacement for a regular oral care routine of twice-daily brushing and daily flossing. So even if your dentist recommends or prescribes a mouthwash, you still need to follow your complete oral care routine to maintain good dental health.