Count() is an extension method introduced by LINQ while the Count property is part of the List itself (derived from ICollection). Internally though, LINQ checks if your IEnumerable implements ICollection and if it does it uses the Count property. So at the end of the day, there's no difference which one you use for a List.
To prove my point further, here's the code from Reflector for Enumerable.Count()
public static int Count<TSource>(this IEnumerable<TSource> source)
{
if (source == null)
{
throw Error.ArgumentNull("source");
}
ICollection<TSource> is2 = source as ICollection<TSource>;
if (is2 != null)
{
return is2.Count;
}
int num = 0;
using (IEnumerator<TSource> enumerator = source.GetEnumerator())
{
while (enumerator.MoveNext())
{
num++;
}
}
return num;
}