The efficacy of azoxystrobin was evaluated in the presence of mycotoxigenic fungi and relative mycotoxins in Italian paddy rice during the growing season in the field. Three experimental fields were considered and the applied experimental design was a strip plot with three replicates; rice samples were collected at four different growing stages. The efficacy of the fungicide treatment on rice fungal population was demonstrated with around 20% less total fungal incidence in sprayed samples compared to untreated ones; the same decrease was noted also in Fusarium spp. species but not in Aspergillus versicolor. Of the mycotoxins considered, ochratoxin A (OTA) and aflatoxins (AFBs) were never detected, deoxynivalenol (DON) was found in 46% of samples at levels always lower than 100 µg/kg, while sterigmatocystin (STC) occurred in all the paddy rice samples collected after flowering, with a maximum value of 15.5 µg/kg. Treatment with azoxystrobin was not effective in reducing DON contamination, but it had an important and significant effect on STC content, showing a decrease of 67% in the sprayed samples.