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A MkIV Brewer spectrophotometer has been operating in Athens since 2004. Direct-sun measurements originally scheduled for nitrogen dioxide retrievals were reprocessed to provide aerosol optical depths (AODs) at a wavelength of about 440 nm. A novel retrieval algorithm was specifically developed and the resulting AODs were compared to those obtained from a collocated Cimel filter radiometer belonging to the Aerosol Robotic Network (AERONET). The series are perfectly correlated, with Pearson’s correlation coefficients being as large as 0.996 and with 90% of AOD deviations between the two instruments being within the World Meteorological Organisation (WMO) traceability limits. In order to reach such a high agreement, several instrumental factors impacting the quality of the Brewer retrievals must be taken into account, including sensitivity to the internal temperature, and the state of the external optics and pointing accuracy must be carefully checked. Furthermore, the long-term radiometric stability of the Brewer was investigated and the performances of in situ Langley extrapolations as a way to track the absolute calibration of the Brewer were assessed. Other sources of error, such as slight shifts of the wavelength scale, are discussed and some recommendations to Brewer operators are drawn. Although MkIV Brewers are rarely employed to retrieve AODs in the visible range, they represent a key source of information about aerosol changes in the past three decades and a potential worldwide network for present and future coordinated AOD measurements. Moreover, a better understanding of the AOD retrieval at visible wavelengths will also contribute in improving similar techniques in the more challenging UV range.