This study reports the analysis of Si in airborne particulate matter by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) as well as X-ray fluorescence (XRF). It was found that Si concentration in airborne particulates collected on PTFE-membrane filters could be accurately determined with a laser beam operated at 160 mJ free running mode, 6.5 mm defocusing distance and 0.8 1/min carrier gas flow rate during the LA-ICP-MS measurement. Standard filters prepared by NIST SRM 1648 urban particulates were used for both XRF and LA-ICP-MS not only to establish the calibration curves of Si, but also to examine the proposed method's effectiveness. The capability of applying both methods for natural sample analysis was also examined. Particulate loaded filter samples collected from a heavily polluted metropolitan area of Kaoshiung, Taiwan were initially measured by XRF, then by LA-ICP-MS. An intercomparison between them was thus performed. As a result, both XRF and LA-ICP-MS proved to be the valid analytical methods for directly determining Si concentrations in airborne particulates on PTFE membrane filters.