The construction and electrochemical response characteristics of a screen‐printed electrode (SPE) for the determination of dodecyltrimethylammonium bromide (DTAB) are described. The sensor was based on the use of DTA‐tetraphenylborate ion association complex as an electroactive material in screen‐printed electrode with dioctylsebacate (DOS) as a solvent mediator. In aqueous solution of pH 3, the sensor displayed a stable response for six months with reproducible potential and linear response for surfactant over the concentration range 1.20 × 10−2−5.6 × 10−7 mol L−1 at 25 °C with Nernstian slope of 55.95 ± 0.58 mV decade−1 for detection limit of 6.8 x 10−6 mol L−1. The response time was 6–10 s. The selectivity coefficients indicate excellent selectivity for DTAB over many common cations (e.g. Mg2+, Na+, K+, Co2+, Ni2+ , Ca2+, Cl−, I−, SO4−2 and cetylpyridinium chloride (CPC). The sensor was used successfully for the determining of DTAB in pure form and water samples with average recoveries of 99.98, 98.78, and 99.99%. Copyright © 2011 John Wiley & Sons, Ltd.