The photocatalytic activity of N-doped TiO2 nanoparticles to degrade metoprolol (MET) has been investigated. The materials were synthesized via sol-gel method and characterized using different techniques. All materials revealed the formation of anatase phase, with a band gap energy close to 3.12 eV, which suggests that the N doping did not cause substantial variations as compared to pure TiO2. However, the TiO2-5%N photocatalyst exhibited a reduction in nanoparticle size and a surface area 0.4-fold larger than undoped TiO2. The influence of pH, catalyst concentration, and doping percentage was investigated through a Box-Behnken experimental design. Under the best conditions (0.5 g L−1 of TiO2-5%N, solution pH 6.0), 98% MET degradation and 42% mineralization could be achieved, and the process by-products were non-toxic to Artemia salina. Display omitted •Nitrogen doping promoted the formation of oxygen and Ti3+ surface defects in TiO2.•The system exhibited enhanced removal of refractory organic pollutants.•A Box-Behnken factorial design was employed as a statistical tool for metoprolol degradation.•Toxicity assessments with Artemia salina showed a satisfactory response to secondary effluent treatment enriched with MET.