Orthogonal array design (OAD) and electronic pressure programming (EPP) using built‐in electronic pressure control (EPC) has been employed to optimize gas chromatographic (GC) conditions to improve the separation and detection of the isomers of 4‐nonylphenol whose high toxicity towards marine life is well documented. Seven GC parameters have been examined by the OAD, namely carrier gas pressure program, initial oven temperature, time duration of initial oven temperature, final oven temperature, solvent effect, purge‐on time, and two different oven heating rates. Two responses, normalized peak area (NPA) and number of distinguishable peaks (NDP), were used to evaluate the suitability of OAD for the optimization of GC performance. A good correlation between two responses was established. The optimization of these parameters in the analysis of 4‐nonylphenol demonstrates the applicability of the OAD and EPC for environmental analysis by GC. © 1996 John Wiley & Sons, Inc.