That depends on what you call the primary/secondary. Some folks call the higher voltage side of the transformer the primary irrespective of the direction of current flow.
I am not aware of any formal definition of how to know which side is primary and which side is secondary, in all applications. A physics book will tell you that the source of energy is on the primary side. And in most applications under the scope of the NEC, that is also the side toward the utility and also the side that is at higher voltage.
However, in the case of backfed transformers, it is a little less clear. Consider a PV application where a 208V to 480V transformer is used, with the inverters on the 480V side and the building is on the 208V side. Which side is primary? Which side should be governed by the NEC rules for "transformer secondary conductors"? I could take a poll of all of you, and I'd get half of the answers opposite the other half.
Larger conductors are typically (always?) on the lower voltage side.
That usually is precisely the reason why the transformers are used in the first place. To reduce the wire for long distance circuits. Voltage you pay for with plastic, current you pay for with metal.
Specifically, the conductive part of the larger conductors is larger. It very well may be that the wires with the larger overall OD are on the higher voltage side, because of the medium voltage insulation.
One counterexample is if the minimum medium voltage cable size per the utility standards is 1/0. If you are using it for 100A on the secondary low voltage side, you might have #2 on the secondary and #1/0 on the primary.