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Insulation. Styrofoam insulates much more effectively than plastic, which means your cold drinks stay colder longer and your hot drinks stay hotter. Plastic cups are not recommended for hot drinks, and they do not have the insulation properties of Styrofoam.
If price is your main concern, plastic is the less costly option. It is lighter, which makes manufacturing and shipping less expensive. Styrofoam is a little more expensive to purchase, but it does double as a hot and cold drink cup, so it may be more cost-effective in the end, depending on your intended use.