The presented studies have focused on application of a new anatase-phase TiO2 for decomposition of azo dye Acid Red 18 in a photocatalytic membrane reactor (PMR) combining photocatalysis and direct contact membrane distillation (DCMD). The catalyst used in this study (A-700-1h) was prepared from TiO2 obtained directly from the production line (sulfate technology) at the Chemical Factory "Police" by calcination for 1 h at 973 K in air. It was found that the effectiveness of the model dye degradation increased with increasing the value of all the parameters investigated, that is, feed flow rate, reaction temperature and catalyst loading. The addition of TiO2 to a feed did not affect the permeate flux, regardless of the catalyst loading applied. The effectiveness of azo dye removal in the PMR was compared with the effectiveness obtained during photocatalysis alone conducted in the recirculation and batch modes. Taking into account both, the rate of azo dye degradation and the quality of the product, the most beneficial configuration seems to be the PMR.