Some of the largest unit discharge flood peaks in the stream gaging records of the U.S. Geological Survey (USGS) have occurred in Puerto Rico. Many of these flood peaks are associated with tropical cyclones. Hurricane Georges, which passed directly over the island on 21–22 September 1998, produced record flood peaks at numerous USGS stations in Puerto Rico. The hydrology and hydrometeorology of extreme flood response in Puerto Rico are examined through analyses of rainfall, based on Weather Surveillance Radar–1988 Doppler (WSR‐88D) radar reflectivity observations and USGS rain gage observations and discharge from USGS stream gaging stations. Peak rainfall accumulations of more than 700 mm occurred in the central mountain region of the island. The largest unit discharge flood peaks, however, were located in the eastern portion of the island in areas with smaller storm total rainfall accumulations but markedly larger rainfall rates at 5–60 min timescale. Orographic precipitation mechanisms played an important role in rainfall distribution over the island of Puerto Rico. Amplification of rainfall accumulations was associated with areas of upslope motion. Elevated low‐level cloud water content in regions of upslope motion played an important role in the maximum rainfall accumulations in the central mountain region of Puerto Rico. The largest unit discharge flood peaks, however, were produced by a decaying eye wall mesovortex, which resulted in a 30–45 min period of extreme rainfall rates over the eastern portion of the island. This storm element was responsible for the record flood peak of the Río Grande de Lóiza. The role of terrain in development and evolution of the eye wall mesovortex is unclear but is of fundamental importance for assessing extreme flood response from the storm. Hydrologic response is examined through analyses of rainfall and discharge from five pairs of drainage basins, extending from east to west over the island. These analyses point to the importance of short‐term rainfall rates for extreme flood response. The hydrologic response of Puerto Rico is compared with two other extreme flood environments, the central Appalachians and Edwards Plateau of Texas. These analyses suggest that the high rainfall environment of Puerto Rico is linked to the development of a hydraulically efficient drainage system.