This paper proposes a novel strategy to enhance selectivity and sensitivity in CE, using supported liquid membrane (SLM) and off-line SPE simultaneously. The determination of ochratoxin A (OA) in wine has been used to demonstrate the potential of this methodology. In the S LM step, the donor phase (either a 20 ml, volume of a standard solution at pH 1 or a wine sample at pH 8) was placed in a vial, where a micromembrane extraction unit accommodating the acceptor phase (1 mL water, pH 11) in its lumen was immersed. The SLM was constructed by impregnating a porous Fluoropore Teflon (PTFE) membrane with a water-immiscible organic solvent (octanol). In the off-line SPE step, the nonpolar sorbent (C-18, 4 mg) selectively retained the target ochratoxin, enabling small volumes of acceptor phase (1 mL) to be introduced. The captured analytes were eluted in a small volume of methanol (0.1 mL). This procedure resulted in sample cleanup and concentration enhancement. The method was evaluated for accuracy and precision, and its RSD found to be 5%. The LODs for OA in the standard solutions and wine samples were 0.5 and 30 mu g/L, respectively. The results obtained demonstrate that SLM combined with off-line is a good alternative to the use of immunoaffinity columns prior to CE analysis.