Brannerite‐type layered vanadomolybdate, KVMoO6, was synthesized by sol–gel method using ethylene glycol as gelating agent. Its silver‐ and nitrogen‐doped analogues were prepared by ion exchange and solid state methods, respectively. All compounds were characterized by powder X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), energy dispersive spectroscopy (EDS), Fourier transform IR spectroscopy (FT‐IR), and UV–vis diffuse reflectance spectra. The bandgap energy of all compounds was obtained from their diffuse reflectance spectra. Bandgap was reduced considerably upon silver and nitrogen doping in KVMoO6. The photocatalytic activity of parent and doped samples was studied by degradation of methylene blue. The nitrogen‐doped KVMoO6 shows higher photocatalytic activity against the degradation of methylene blue. The stability and reusability of the nitrogen‐doped KVMoO6 were investigated. N‐doped KVMoO6 is a potential catalytic material for cleaning wastewater.