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I'm surprised no one has created this thread yet. Now, let it be clear that this thread is about the PRC's road system; if you're looking for roads in Taiwan or Hong Kong, then you're in the wrong place.
So here's a basic rundown of roads in China. China's expressway system is called the National Trunk Highway System (中国国家干线公路系统). It contains nationally- and provincially-maintained expressways, prefixed with G (for 国/guo, the Chinese word for "country") and S (for 省/sheng, the Chinese word for "province"). It has 142,500 km of expressway, which is the largest such system in the world, and nearly twice the length of the interstate highway system. It is also the fastest-growing expressway system in the world. It expands so fast, and the route numbers change so easily, in fact, that Google Maps isn't really accurate sometimes. A more accurate option would be Baidu Maps and QQ Maps, and as a bonus, they both have equivalents of GSV too (though I would caution against using the latter's, as it uses Flash). Almost all of it is tolled (for a price not cheap), and there are toll booths at provincial boundaries, even on the non-expressways. And most of the time, they remain outside downtowns of cities.
The national expressways are also known as the "71118 network" (formerly 7918, until two more were added over the years). This is because it consists of 7 radial expressways, 11 N-S expressways, and 18 E-W expressways. G1-G7 are radial expressways from Beijing to other major cities in China, G11-G85 are the N-S expressways from east to west, G10-G80 are the E-W expressways from north to south, and G91-G99 are large beltway too large to be auxiliary routes. Note that the numbering pattern is in the opposite direction as the interstate highway system, and in the same direction as US highways.
There are also auxiliary and suffixed routes, formed by adding 2 extra digits or a suffix to the parent route number respectively. 0 followed by a digit 1-9 indicates a beltway (unlike here, most beltways in China are complete). 1 followed by a digit 1-9 indicates a spur route (these can be pretty long, actually, as all are supposed to cross a provincial border at least once). Suffixed routes are given an additional digit at the end (e.g. G15W2) if there are more than one on a parent route.
(More recently, suffixed routes have been replaced by auxiliary routes with 2 followed by a digit 1-9 after the parent router's number. Even more recently, the auxiliary routes have been renumbered so that there are no duplicates. For example, there used to be four G1501s, but now there is only one, and the rest are G1502, G1502, and G1504. These changes are so new that no mapping agencies, not even Chinese ones, have reflected these changes, and they seem to, for the most part, only exist on paper.)
Here is a map of the NTHS:

Provincial expressways work in much of the same way as national expressways, except that they are prefixed with S, have a yellow banner instead of a red one, and are contained within a single province much like state highways in the US. The numbering system of S-routes depends on which province you are in; in Fujian Province, they can even be 4-digit auxiliary routes. Many of these have been converted into auxiliary G-routes once extended past a provincial boundary.
Oh, and one more thing. Due to legal restrictions on Chinese GPS data, mapping agencies outside of the PRC must misalign their maps of mainland China. This means that satellite imagery does not align with the maps, and that roads get cut off at international borders. Know this before ranting here. And please try not to make this thread political, for the love of God.
Helpful links:
Expressways in China -
https://en.wikipedia.org/wiki/Expressways_of_ChinaList of NTHS expressways -
https://en.wikipedia.org/wiki/List_of_NTHS_ExpresswaysList of NTHS auxiliary expressways -
https://en.wikipedia.org/wiki/List_of_auxiliary_NTHS_ExpresswaysList of provincial expressways of China -
https://en.wikipedia.org/wiki/List_of_Regional_Expressways_of_ChinaTL;DR: Mainland China's road system is so good that it makes ours look like a joke.