Serious environmental problems are exacerbated with economic growth. Pollution control and emission reduction are now challenged, and we have to pay real attention. Pollutant discharge fee (PDF), one of the enforced levy regulations on pollutant discharge in China, was introduced in a new perspective as a direct economic representation of multi-pollutant emission. The DPSIR framework and regression model were constructed to analyze the co-control process of pollutant emission based on the provincial data from 2000 to 2012. The results showed that PDF had a significant and positive relationship with CO2 emission in China during 2000–2012. A special contradiction was found that CO2 emission and PDF increased greatly, verified with empirical analysis, while the pollutant emission reduction target in the 11th and 12th Five-Year Plan (FYP) was achieved for the corresponding periods, which indicated that emission co-control is still unrealized in China. Conversely, the single indicator control of pollutant emission generated by opportunistic behavior of the Chinese government failed to bring real environmental improvement. In addition, PDF can be seen as a mirror for the Environment Tax (ET) to achieve authentic emission reduction and pollution control, even for sustainable development in China.