The Clouds and the Earth’s Radiant Energy System (CERES) is a new National Aeronautics and Space Administration space-borne measurement project for monitoring the radiation environment of the earth–atmosphere system. The first CERES instrument was launched into space on board the Tropical Rainfall Measuring Mission (TRMM) satellite on 27 November 1997. The purpose of this paper is 1) to describe the initial validation of the new CERES/TRMM Earth Radiation Budget Experiment (ERBE)–like monthly mean clear-sky longwave (CLW) dataset and 2) to demonstrate the scientific benefit of this new dataset through a data application study on the 1998 El Niño–Southern Oscillation (ENSO) episode. The initial validation of the CERES CLW data is carried out based on comparisons with both historical ERBE observations and radiative transfer simulations. While the observed CERES CLWs are initially larger than the historical ERBE record during the first part of the 1998 ENSO event, these differences are diminished by the end of the ENSO event in July 1998. These unique ENSO-related CLW radiation signatures are captured well by the radiative transfer model simulations. These results demonstrate that the new CERES CLW fluxes are theoretically consistent with the underlying physics of the atmosphere. A CERES data application study is performed to examine the relationship between the CERES CLW anomaly and changes in sea surface temperature (SST) and atmospheric column precipitable water content (PWC) during the January 1998 ENSO event. While the changes in the SST pattern are basically uncorrelated with changes in the CLW field, a negative correlation is found between the PWC anomaly and the changes in the CLW radiation field. These observed features point to 1) the significant role of the water vapor field in modulating the tropical outgoing CLW radiation field during the 1998 ENSO event and 2) the important effects of water vapor absorption in decoupling the top of the atmosphere tropical outgoing CLW radiation from the surface upward CLW field.