After some searching, I believe I know how VAG achieves the fuel efficiency advantage of the Golf GTI compared to the Polo WRC (by the way, the Scirocco 2l TSI with 210 hp has a CO2 emission of almost 172 g, which is nearly as high as the WRC Polo's 174 g): simply by using the currently popular "BlueMotion" features.
The start-stop function primarily reduces fuel consumption in urban driving by automatically shutting off the engine during periods of inactivity.
In addition to that, there's also what's known as recuperation:
When braking, the alternator voltage is disconnected, which tends to overcharge the battery. During acceleration, the alternator is switched off, and the electrical load is solely supplied by the battery. This allows you to achieve the desired acceleration or speed with slightly less fuel consumption.
This requires expensive specialized batteries, and the electrical components may not necessarily last as long under the constantly fluctuating onboard voltage that is typically encountered.
See also
http://www.volkswagen.de/de/Volkswagen/InnovationTechnik/technik-lexikon/rekuperation.html.
Overall, I believe these are more like "tricks" for optimizing fuel consumption, which can significantly reduce the "normal" consumption and save a few euros on CO2-based taxes. However, with anticipatory driving that involves minimal braking and limited stop-and-go situations, the actual fuel consumption probably won't be reduced as much as the catalog data suggests.