We present and discuss data from petrographic observation at the optical microscope, electron microprobe analyses on selected glass shards, and trace-element analyses on 14 mortar aggregates collected at the ancient harbors and other maritime structures of Latium and Campania, spanning the third century BCE through the second CE, aimed at identify the volcanic products employed in the concretes and their area of exploitation.According to Latin author Vitruvius assertion about the ubiquitous use of Campanian pozzolan in the ancient Roman sea-water concretes, results of this study show a very selective and homogeneous choice in the material employed to produce the concretes for the different investigated maritime structures, evidencing three main pumice compositions, all corresponding to those of the products of the post-Neapolitan Yellow Tuff activity of the Phlegraean Fields, and a systematic use of the local Neapolitan Yellow Tuff to produce the coarse aggregate of these concretes. However, mixing with local products of the Colli Albani volcanic district, located 20km east of Rome, has been evidenced at two fishponds of Latium, in Punta della Vipera and Torre Astura. Based on these petrographic and geochemical data, we conclude that the selective use of pozzolan from Campania, rather than of unproved different chemical properties, was the consequence of a series of logistic, economic, industrial and historical reasons.