NameValueCollection vs Dictionary<string,string>

They aren't semantically identical. The NameValueCollection can have duplicate keys while the Dictionary cannot.

Personally if you don't have duplicate keys, then I would stick with the Dictionary. It's more modern, uses IEnumerable<> which makes it easy to mingle with Linq queries. You can even create a Dictionary using the Linq ToDictionary() method.

NameValueCollection is string typed whereas Dictionary leverages generics to allow type variance. See Benefits of Generics.

Dictionary will be much faster. NameValueCollection allows duplicate keys. Which could be bad in certain situations, or desired in other. Dictionary does not allow duplicate keys.

From: http://msdn.microsoft.com/en-us/library/xfhwa508.aspx

The Dictionary<(Of <(TKey, TValue>)>) generic class provides a mapping from a set of keys to a set of values. Each addition to the dictionary consists of a value and its associated key. Retrieving a value by using its key is very fast, close to O(1), because the Dictionary<(Of <(TKey, TValue>)>) class is implemented as a hash table.