Abstract: The molecular character of atmospheric particulate matter is of prime importance when interpreting air pollution trends and its subsequent influence on environmental monitoring and preventative conservation. The known methods of estimating the molecular composition normally involve elemental analysis of particles (both as bulk and computer controlled analyses of single particles) with subsequent multivariate analyses to clusterise the elements in groups of elements that are closely related to each other. With this approach one can at best suggest associations. Evidently the application of molecular spectroscopy in addition to elemental concentration profiles would provide intimate information regarding the nature of the particles and consequently their fate. This paper gives an overview of research performed in our laboratory and describes the optimisation of experimental parameters to use scanning electron microscopy with energy-dispersive X-ray detection (SEM/EDX) or electron probe X-ray microanalysis (EPXMA) in parallel with micro-Raman Spectrometry (MRS) to investigate single environmental particles. The challenges associated with the two stand-alone techniques are revealed and consequently those posed with an interfaced approach are discussed. Preliminary results, of an initial investigation of the SEM/EDX interfaced with MRS to ultra-fine heterogeneous environmental particles, are given.