Herein, a simple assembly was designed via a capillary and a funnel-like cap to achieve liquid-gas compound pendant drop (CPD) microextraction with great convenience. Due to the increased contact area and adhesion force between the capillary tip and the drop, the proposed method provides considerable flexibility in producing CPDs with different air bubble sizes. Four pesticides were chosen as model analytes to evaluate the proposed method. By using a 1 μL chlorobenzene droplet containing a 1 μL air bubble at a stirring rate of 700 rpm, a 70 to 135-fold enrichment of pesticides was obtained within 3.4 minutes. As compared with a typical SDME, the proposed method showed a 2-fold increase of enrichment factors and a 4-fold decrease of extraction time. Improvement of the extraction efficiency could be ascribed to the increased surface area of the droplet, and the thin film phenomena further improved the extraction kinetics through effective agitation. The results indicate that CPD microextraction could serve as a promising sample pretreatment method for automated high-throughput analyses in a wide variety of research areas.