The National Meteorological Satellite Center/Korean Meteorological Administration (NMSC/KMA) receives data directly from low Earth orbit (LEO) satellites (including NOAA-18,19; MetOp-A,B; and Suomi-NPP), and generates Level 2 products (e.g., temperature and humidity profile) in near real time. Total precipitable water (TPW) and layer precipitable water (LPW) are also generated using the retrieved humidity profiles. Today, forecasters need meteorologically-significant data fields composited from all available data sources, not multiple maps of observations from individual sources. Hence, TPW and LPW are reproduced using the optimal interpolation (OI) method with numerical weather prediction (NWP) data, in order to generate composite precipitable water (PW) products. In the OI procedure, PW data retrieved from the LEO satellites serve as observation data, while PW data from NWP serve as background data. Error covariances are estimated using a new approach, which considers correlations between observation errors to describe the characteristics of the errors better. Both background and observation error covariance matrices may have non-zero off-diagonal components. The composite PW products are validated using radiosonde data. The validation results for optimally-interpolated LPW (OI LPW) are much better than those for optimally-interpolated TPW (OI TPW). Generally, the OI LPW validation results are better than those for observation and background data; OI LPW data are ~5–10% more accurate than background data. Optimally-interpolated PW (OI PW) fields are applied to the correction of NWP forecast fields and the prediction of severe weather.