Two sample preparation methods for the determination of dibenzylamine (DBA) in artificial saliva leachates from rubber baby bottle nipples have been developed, using either solid-phase extraction (SPE) with N-vinylpyrrolidone/divinylbenzene as the sorbent or solid-phase microextraction (SPME) with a polyacrylate coated fiber. The baby bottle nipples were immersed into artificial saliva for 6 h, a part of the solution was brought to pH 9 for SPE or pH 10 for SPME and the analyte was extracted by SPE or SPME. After elution with ethyl acetate (SPE) or thermal desorption (SPME) DBA was determined by gas chromatography with mass spectrometric detection. The main advantages of SPE were superior ruggedness and stability as well as the possibility of preparing several samples simultaneously. SPME offered a greater sensitivity and much smaller sample volumes were required. The results obtained for the investigated rubber baby bottle nipples were almost identical with both the methods showing deviations of less than 3%.