Bandgap narrowing and a more positive valence band (VB) potential are generally considered to be effective methods for improving visible-light-driven photocatalysts because of the significant enhancement of visible-light absorption and oxidation ability. Herein, an approach is reported for the synthesis of a novel visible-light-driven high performance polymer photocatalyst based on band structure control and nonmetal and metal ion codoping, that is, C and Fe-codoped as a model, by a simple thermal conversion method. The results indicate that compared to pristine graphitic carbon nitride (g-C3N4), C+Fe-codoped g-C3N4 shows a narrower bandgap and remarkable positively shifted VB; as a result the light-absorption range was expanded and the oxidation capability was increased. Experimental results show that the catalytic efficiency of C+Fe-codoped g-C3N4 for photodegradation of rhodamine B (RhB) increased 14 times, compared with pristine g-C3N4 under visible-light absorption at λ>420 nm. The synergistic enhancement in C+Fe-codoped g-C3N4 photocatalyst could be attributed to the following features: 1) C+Fe-codoping of g-C3N4 tuned the bandgap and improved visible-light absorption; 2) the porous lamellar structure and decreased particle size could provide a high surface area and greatly improve photogenerated charge separation and electron transfer; and 3) both increased electrical conductivity and a more positive VB ensured the superior electron-transport property and high oxidation capability. The results imply that a high-performance photocatalyst can be obtained by combining bandgap control and doping modification; this may provide a basic concept for the rational design of high performance polymer photocatalysts with reasonable electronic structures for unique photochemical reaction.