Dictionary is typed (so valuetypes don't need boxing), a Hashtable isn't (so valuetypes need boxing). Hashtable has a nicer way of obtaining a value than dictionary IMHO, because it always knows the value is an object. Though if you're using .NET 3.5, it's easy to write an extension method for dictionary to get similar behavior.
If you need multiple values per key, check out my sourcecode of MultiValueDictionary here: multimap in .NET