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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.
The plastic is polymer. Polymers can be thermal and electrical insulators. For example, pots and pans handles are made of polymers, so are insulated cups, coolers, and microwave cookware. Remember that styrofoam is a trademarked name of the Dow chemical company for its brand of polystrene foam. It works by reducing a process known as heat transfer.