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In the purest sense, both of these terms could be defined as lacking any scent or fragrance. When they’re used to describe a commercial product, “fragrance-free” will generally mean that no fragrance has been included in the formula. “Unscented” will usually mean that no fragrance has been included in the formula to make that product smell scented.
When you see words like fragrance, perfume, parfum or fragrance oils listed on a label, they represent a synthetic chemical or mix of chemicals. Manufacturers will often add a synthetic fragrance for the sole purpose of masking or covering up unpleasant smells from the raw ingredients they used to make their products; these products, containing a masking fragrance, will then be labeled as unscented. Be on the watch!
Reading all the labels and checking the ingredient listing carefully is the only way you can know if the various products you use are fragrance-free.