At the beginning of the study, our hypothesis was that visiting certain microenvironments (MEs) is one of the most important determinants of personal exposure to ultrafine particles (UFP) and that moving between microenvironments significantly differentiates exposure. The overall aim of this study is to perform relevant exposure measurements to extend our knowledge on environmental exposure to UFP in urban environments. The UFP concentrations in different urban MEs were measured by personal monitoring in repeated sampling campaigns along a fixed route. The measurement runs were performed on one-week periods and at different times of day (AM: 08.00–10.30; PM: 16.00–18.30) and repeated in different periods of the year (winter, spring, summer, and autumn) for a total of 56 runs (>110 h). Measurements included on-line monitoring of the UFP particle number concentration (PNC), mean diameter (mean-d) and lung-deposited surface-area (LDSA). Additionally, the PNC, particle mass concentration (PMC) profiles for quasi-ultrafine particles (QUFP; PM0.25) were estimated. A significant seasonal difference in the PNC and PMC, mean diameter and surface area was observed as well as between different times of the day and days of the week. In addition, differences in the UFP concentrations were also found in each ME, and there were specific mean-diameter and surface area concentrations. In general, the mean particle diameters showed an inverse relationship with the PNC, while the LDSA had the opposite behaviour. Appreciable differences among all MEs and monitoring periods were observed; the concentration patterns and variations seemed related to the typical sources of urban pollutants (traffic), proximity to sources and time of day. The highest exposures were observed for walking or biking along high-trafficked routes and while using public buses. The UFP exposure levels in modern cars, equipped with high-efficiency filters and in air recirculation mode, were significantly lower.