Novel solid-phase microextraction (SPME) fibres containing methyl, ethyl, butyl acrylate and methacrylate were first prepared by a sol-gel technique and investigated for determination of selected organoarsenic compounds (lewisite, methyldichloroarsine, phenyldichloroarsine, diphenylchloroarsine and triphenylarsine) from water samples. The influence of sorption and desorption temperature and time for extraction efficiency were examined. The best new fibre coatings (methyl acrylate (MA), methyl methacrylate (MMA) and combination of methyl acrylate and methacrylate (MA/MMA)) for analysis of organoarsenic compounds were selected and compared with commercial fibres. The distribution coefficients Kfs were determined for the best novel fibres and for absorption commercial fibres. The highest Kfs value were obtained for MA/MMA and MMA fibres and were respectively 9458 and 6561 for lewisite and 6458 and 5884 for triphenylarsine. The limit of detection and quantification were determined for the three laboratory obtained fibres (MA, MMA and MA/MMA). LODs for tested fibres, at a signal-to-noise of 3, were 0.03-0.3 ng mL(-1). LOQs for selected coatings, at signal-to-noise of 10, were 0.1-0.8 ng mL(-1). The relative standard deviations (RSD) for all measurements were 4.3-6.5% (n=9) and relative errors were 2.5-5%. The laboratory obtained fibres were used for environmental analysis of pore water samples from the Baltic Sea.