It depends on the form, and also its role/moveset. Rotom-Wash, for example, is commonly used as a defensive pivot, as it has a good defensive typing, and can hit ground types with Hydro Pump. A Bold Nature would be best for this.
For more offensive forms, such as Rotom-Heat, pick a nature that best fits its moveset. For example, a special tank Rotom should have a Modest Nature, and a Choice Scarf Rotom should have Timid.
So, the natures you can give Rotom can vary, but for competitive, you should probably only be considering Modest, Timid, Bold, and Calm.
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