Using polystyrene certified reference materials (CRMs) whose molecular weights range from 500 to 2400, we investigated the reliability of molecular weight determination by size-exclusion chromatography (SEC), SEC coupled with multi-angle light scattering detection (SEC-MALS), conventional static light scattering (SLS), matrix-assisted laser desorption/inonization time-of-flight mass spectrometry (MALDI-TOFMS), and H-1 NMR. Average molecular weights determined by these methods were compared with the certified values which were determined by supercritical fluids chromatography with relative standard uncertainty less than 1%. The comparison showed that recent SEC with calibration constructed by uniform polystyrenes can provide just the same average molecular weights as certified ones within the standard uncertainty. 1H NMR was also found to be a powerful technique to determine number-average molecular weight accurately. Average molecular weights measured by SEC-MALS and SLS nearly agreed with certified values except for lower molecular weights. Although MALDI-TOFMS provided average molecular weights in agreement with certified values, the polydispersity given by MALDI-TCFMS were found to be very small for all the polystyrenes. (C) 2004 Elsevier Ltd. All rights reserved.