First, about documentation. This is very confusing documentation.
OrderedQ says
By default, OrderedQ uses canonical order as described in the notes
for Sort.
then going to Sort one sees this
Sort[list,p] applies the ordering function p to pairs of elements in
list to determine whether they are in order. The default function p is
Order.
Notice that the default is Order. Then going to Order it says
Order uses canonical order as described in the notes for Sort.
It is a circle, where one page sends to another to another and we end up we were started.
But the issue is due to not using numerical input. If you do this
x=1/6 (3-Sqrt[5]); (* 0.127322 *)
y=2/3; (* 0.666667 *)
OrderedQ[{x,y}]

But now if we do this
x=1/6 (3.-Sqrt[5]);
y=2/3;
OrderedQ[{x,y}]

And this now matches Less,
Less[x,y]

OrderedQ does not use numerical method to check ordering unless input is numerical. When it is exact, it works as it says in Possible issues
OrderedQ by default works structurally, not by numerical value:
To make it give same value as Less without making it numerical, do
x=1/6 (3-Sqrt[5])
y=2/3;
OrderedQ[{x,y},Less]

So the way you used it, the ordering was not based on numerical value of input. Agree, that this is a bit confusing function to use.