Herein, Fe-doped C3N4 high-performance photocatalysts, synthesized by a facile and cost effective heat stirring method, were investigated systematically using powder X-ray diffraction (XRD), Fourier transform infrared (FTIR), scanning electron microscopy (SEM) and Brunauer–Emmett–Teller (BET) surface area measurement, X-ray photoelectron (XPS), UV–Vis diffusion reflectance (DRS) and photoluminescence (PL) spectroscopy. The results showed that Fe ions incorporated into a g-C3N4 nanosheet in both +3 and +2 oxidation states and in interstitial configuration. Absorption edge shifted slightly toward the red light along with an increase of absorbance in the wavelength range of 430–570 nm. Specific surface area increased with the incorporation of Fe into g-C3N4 lattice, reaching the highest value at the sample doped with 7 mol% Fe (FeCN7). A sharp decrease in PL intensity with increasing Fe content is an indirect evidence showing that electron-hole pair recombination rate decreased. Interestingly, Fe-doped g-C3N4 nanosheets present a superior photocatalytic activity compared to pure g-C3N4 in decomposing RhB solution. FeCN7 sample exhibits the highest photocatalytic efficiency, decomposing almost completely RhB 10 ppm solution after 30 min of xenon lamp illumination with a reaction rate approximately ten times greater than that of pure g-C3N4 nanosheet. This is in an agreement with the BET measurement and photoluminescence result which shows that FeCN7 possesses the largest specific surface area and low electron-hole recombination rate. The mechanism of photocatalytic enhancement is mainly explained through the charge transfer processes related to Fe2+/Fe3+ impurity in g-C3N4 crystal lattice.