Guam -- 542 km
The previous answer, Honshu, is the largest Island of Japan, but it is not one of the Mariana Islands. Other islands in the Marianas are:
Agrihan - 47 km2
Aguijan - 7 km2
Alamagan - 11 km2
Amatahan - 32 km2
Asuncion - 7.4 km2
Farallon de Medinilla - 0.9 km2
Farallon de Pajaros - 2 km2
Guguan - 4 km2
Maug Islands (actually, 3 islets) - total area is < 2 km2
Pagan - 48 km2
Rota - 85 km2
Saipan - 115 km2
Sarigan - 5 km2
Tinian - 101 km2
Some websites will cite Saipan as being the largest of these islands. Saipan is the largest of the Northern Marianas (which is a Commonwealth), but not of the total chain.