A large number of grid-connected Photovoltaic parks of different scales have been operating worldwide for more than two decades. Systems’ performance varies with time, and an important factor that influences PV performance is dust and ambient aerosols. Dust accumulation has significant effects depending the region, and—on the other hand—understanding the role of absorption or scattering in particular wavelengths from aerosols is a challenging task. This paper focuses on performance analysis of a grid-connected PV system in Central Greece, aiming to study these effects. The methodology of analysis follows three directions, namely, PR computations, use of mathematical model’s prediction as reference value, and normalized efficiency calculation. These metrics are correlated with the levels of dust accumulation on PV panels’ surfaces and the ambient aerosol mass concentration. The results show that only heavily soiled surfaces have significant impact on PV performance and, particularly, a decrease of 5.6%. On the other hand, light or medium soiling have negligible impact on PV performance. On the other hand, the impact of ambient aerosol concentration levels on PV efficiency is more complex and requires further study. Aerosol scattering of different wavelengths can possibly affect PV efficiency, however, this fact may be related to the specific spectral response of PV cells.