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I'd imagine the caffeine content would be negligible. The nutritional information for several instant hot cocoa brands (Hershey, Nestle-Carnation) shows that one envelope has about the same amount of caffeine as a cup of decaf coffee - around 5 mg. A normal cup of coffee has around 100 mg.
Disney serves Nestle hot chocolate and it sounds like there's nominal caffeine it it...probably no worse than eating a candy bar! And btw, if you go to the UK in Epcot and ask for "hot cocoa," they'll claim they don't have it but they will happily offer you "hot chocolate" instead!
Also, the free hot chocolate and the hot chocolate you purchase are not the same. We HATED the free stuff but the stuff we purchase was good. My whole group dumped our free stuff and purchased hot chocolate.
The best hot cocoa on the property is at the Italian pavilion at EPCOT. It's just a little stand that sells drinks and bakery items. The cocoa is only $2.50, but it's worth the trip. Yum!
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