A flow injection analysis method for spectrophotometric determination of ammonium in waters produced during underground coal gasification (UCG) of lignite and hard coal was described. The analysis of UCG water samples is very difficult because of their very complicated matrix and colour. Due to a huge content of organic and inorganic substances and intensive colour of samples (sometimes yellow, quite often dark brown or even black), most analytical methods are not suitable for practical application. Flow injection analysis (FIA) is based on diffusion of ammonia through a hydrophobic gas permeable membrane from an alkaline solution stream into an acid-base indicator solution stream. Diffused ammonia causes a colour change of indicator solution, and ammonia is subsequently quantified spectrophotometrically at 590 nm wavelength. The reliability of the results provided by applied method was evaluated by checking validation parameters like accuracy and precision. Accuracy was evaluated by recovery studies using multiple standard addition method. Precision as repeatability was expressed as a coefficient of variation (CV).