RationalePlasma‐based ionization sources play a vital role in rapidly analyzing diverse compounds without extensive sample pretreatment. In contrast to other sources, DC voltage‐based ionizations are more advantageous due to their high analytical sensitivity and good tandem with commercially available mass spectrometers without extra power supplies. However, their performance is at the risk of high current DC voltage and helium flow rate, which poses significant challenges to practical operation and increased expense.MethodsIn this work, we propose a novel focusing plasma desorption ionization (FPDI) in which a visible plasma beam is favorably generated between a conducting wire in a polymeric tube and a counter electrode composed of metal mesh and filter paper drilled with holes. A systematic investigation has been conducted on the influences of the geometry of drilled holes in filter paper, applied DC voltage, helium flow rate, and filter paper size. The optimized system is used to analyze various pesticides in fluid foodstuffs.ResultsCompared to metal mesh and conducting paper as the counter electrode for FPDI‐MS, combining metal mesh and filter paper drilled holes improved the analysis sensitivity by a factor of more than five. By applying the developed protocol for determining pesticides in complex matrixes such as orange juice and milk, a limit of detection as low as 1.3–3.0 ng mL−1 could be achieved.ConclusionsA novel FPDI‐MS technique has been developed by combining metal mesh and filter paper drilled with holes as the counter electrode and sample carrier. The corresponding improvement in analysis sensitivity facilitates the future expansion of FPDI‐MS applications into different pesticides and other compounds in complex matrixes.