Founded in the late 1990s by songwriter Wade Schuman (vocals and harmonica, occasional guitar and other instruments), the band in their formative years also featured mainstays Joe Daley (tuba, sousaphone) and Randy Weinstein (harmonica). Other personnel varied considerably, including not only performers on guitar, drums and sax but also exotic oddities like cimbalom and bass marimba.
Their debut album was recorded over a five-year span and earned positive critical notice. Hazmat Modine was featured on the National Public Radio program "All Things Considered" on October 25, 2006, and on the Australian Broadcasting Corporation program "The Daily Planet" on May 29, 2006.
Their second Hazmat Modine album featured a more stable lineup, though Weinstein has parted ways with the band.
In 2013 Wade Schuman enlisted his friend Erik Della Penna to join the band as a guitarist, co-vocalist and songwriter. Schuman wanted the band to evolve into one that had more vocal harmonies, he was becoming more interested in the long tradition of American songwriting by the likes of Irving Berlin, Fats Waller, Doc Pomus, Hays & Porter. A live album followed in 2014, and a studio album in 2015.