A new passive sampling method was developed and characterized to measure atmospheric volatile methyl siloxanes (VMS). The infrastructure of a commercial passive air sampler (PAS) was used along with XAD-2 resin as the adsorbent. Experimental sampling rates (SR) determined using collocated active and passive samplers ranged between 0.0363 (L5) and 0.0561 (D3) m3/day and agreed well with the theoretical ones. VMS uptake was highly linear for eight weeks. The precision of the method was very good (<10%). Compared to the other PASs used for VMS, the new method has several advantages (i.e., the sampler is much smaller, it has commercially available components, and the solvent requirement, equipment needed for extraction, and steps for sample preparation are minimal) while achieving similar or lower method detection limits. The developed method was applied to investigate the spatial distribution and possible sources of atmospheric VMS in the Izmir region. Field sampling covered 42 sites representing different source and land use areas. ΣVMS concentrations ranged between 41.4 and 981 ng/m3. The dominant VMS was D5 followed by D3 and D4. Spatial distributions indicated that the main VMS sources in the area were urban areas, wastewater treatment plants, and landfills where the VMS-containing products are used and disposed.