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You can iron rayon when it is dry, but it’s easier to do it while the fabric is damp. If your garment is already damp from the wash, then you don’t have to do anything. If it is dry, spray it with a bottle filled with clean water. The rayon doesn’t have to be very wet. It should just be slightly wet to the touch. The rayon can be damaged if you iron it right side out. At the very least, the fabric will become shiny if it makes direct contact with the iron. Always turn the fabric inside out unless you have a pressing cloth between the iron and rayon. If you are starting with a dry garment, you can use a spray bottle to dampen it. If you must iron the fabric right side out, you will need to have something on top of the rayon. You can buy a pressing cloth, or simply use a piece of unbleached or white cotton muslin. Always use the pressing cloth when ironing rayon right side out.
Spray the garment with water. Turn the garment inside out. Put a press cloth between the iron and rayon if you iron it right side out.