Low-temperature and ambient-temperature nonaqueous stacking techniques in capillary electrophoresis (CE) are described for the first time. A low-temperature bath was used to control the temperature from ambient to subzero degrees, by which a novel hyphenated method, low-temperature bath-nonaqueous capillary electrophoresis stacking (LTB-NACE stacking) is demonstrated. 3,4-Methylenedioxymethamphetamine (3,4-MDMA) was determined at a concentration of 4.7 x 10(-6) m (at a 92.1% confidence level) by normal nonaqueous capillary zone electrophoresis (NACZE) and this was improved to 2.6 x 10(-8) m and 5.0 x 10(-9) m, respectively, when the NACZE stacking and LTB-NACZE stacking techniques were applied. The content of 3,4-MDMA in an illicit drug and a suspect urine sample was readily detected. Upon application of the LTB to the separation of isomers the resolution (R) for the separation of 2,3-/3,4-MDMA was improved from 0.6 (LTB, 22degreesC) to 1.6 (LTB, -55degreesC) and for (+)3,4-MDMA/(-)3,4MDMA, from 0.4 (LTB, 25degreesC) to 1.0 (LTB, -10degreesC).