In this study we evaluate the influence of tobacco smoke on the physico-chemical characteristics of PM10 in different environments: outdoors, a smoking room, the same room after a 7-day absence of smokers and in a smoke-free office. The latter office was close to the smoking room, separated by a corridor. The coarse (PM10−2.1) and fine (PM2.1) fractions of PM10 collected in the monitored areas were analysed by scanning electron microscopy, equipped with a thin-window system for X-ray microanalysis (SEM/EDX). Photo-electron spectroscopy (XPS) was used to study the elemental composition of the particulate and to identify the chemical state of atomic species detected. Four clusters of particles for both “fine” and “coarse” fractions were identified: carbonaceous particles, soil erosion particles, Ca-sulphates and metal compound particles. EDX spectra showed that a percentage of carbonaceous particles carried S, Si and metal traces. High-resolution XPS spectra of the C1s region showed a significant greater occurrence of the C–O/C–N functional group in the particulate fine fraction collected in the smoking room compared to that collected outdoors. The carbonaceous component of coarse fraction collected in the smoking room appeared dissimilar from the same component detected in the other areas. After the 7-day absence of smokers this component of the PM10−2.1 fraction was similar to the corresponding coarse fraction collected at the outdoor location. The carbonaceous component of fine fraction collected in the smoking room, containing tobacco smoke products, such as organic carbon and nicotine, was traceable in the neighbouring areas, even several days after suspension of smoking activity.