As best I can tell from a cursory online search, Mel Martinez (R-Fla.) and Ken Salazar (D-Colo.) are tied for being the four Hispanic Senator in U.S. history. Octaviano Larrazolo (1928-29), Dennis Chavez (1935-62), and Joseph Montoya (1964-77), all from New Mexico (the first a Republican and the other two Democrats), are numbers one, two, and three.
On the other hand, my search has been far from thorough, and “Hispanic” is a notoriously slippery term (see here for a slightly facetious example), so I might be mistaken.
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