We report on the characterization of columnar aerosol optical and microphysical properties in the Naples Mediterranean area over a period of five years by the ground-based sun–sky–lunar photometer operating at our observational station in the frame of the AERONET network. Statistical and climatological analyses of daily mean values of aerosol optical depth at 440 nm (AOD440) and Ångström exponent at 440/870 nm (α440/870) allowed for highlighting their typical seasonal behavior. In particular, we observe higher mean values of the AOD440 during summer or spring, which are consistent with an increased frequency of both Saharan dust transport events and biomass burning episodes affecting the measurement area in these periods of the year. Conversely, α440/870 does not show any typical seasonal trend. In order to gain information on the different aerosol contributions along the atmospheric column, the frequency distributions of AOD440 and α440/870 were analyzed and fitted by a superposition of Gaussian functions. The most populated modes are centered at α440/870 = 1.26 ± 0.07 and AOD440 = 0.16 ± 0.01. These values are associated with continental polluted aerosol mixed with sea salt aerosol and correspond to the background conditions typically observed in clear atmospheric conditions. Daily size distributions averaged over each month highlight that the fine aerosol component always prevails over the coarse fraction, except for the few months in which Saharan dust events are particularly frequent. Finally, the mean value of the SSA at 440 nm resulted as 0.94 ± 0.05, while the refractive index real and imaginary part were 1.47 ± 0.07 and (6.5 ± 0.2) × 10−3, respectively. These values are in agreement with those observed in other Mediterranean sites located in Southern Italy, evidencing a rather characteristic feature of the geographical region.