Exposure to ultrafine combustion aerosols such as particulate matter (PM) from residential woodburning, forest fires, cigarette smoke, and traffic emission have been linked to adverse health outcomes. Excitation-emission matrix (EEM) spectroscopy presents a sensitive and cost-effective alternative for analysis of PM organic fraction. However, as with other analytical chemistry methods, the miniaturization is hindered by a solvent extraction step and a need for benchtop instrumentation. We present a methodology for collecting and in-situ analysis of airborne nanoparticles that eliminates labor-intensive sample preparation and miniaturizes the detection platform. Nanoparticles are electrostatically collected onto a transparent substrate coated with solid-phase (SP) solvent—polydimethylsiloxane (PDMS). The PM organic fraction is extracted into PDMS and analyzed in-situ , thus avoiding liquid-phase extraction. In the SP-EEM analysis, we evaluated external and internal excitation schemes. Internal excitation shows the lowest scattering interference but leads to signal masking from PDMS fluorescence for λ<250nm. The external excitation EEM spectra are dependent on the excitation light incident angle; ranges of 30–40° and 55–65° show the best results. SP-EEM spectra of woodsmoke and cigarette smoke samples are in good agreement with the EEM spectra of liquid-phase extracts. The SP-EEM technique can be used to develop wearable sensors for exposure assessments and environmental monitoring.