CaAl-layered double hydroxide (CaAl-LDH), one of anionic functional layered materials, has recently been proposed as potential concrete hardening accelerators. Previous laboratory synthesis shows the necessity of employing a protective nitrogen atmosphere to avoid the formation of large amounts of CaCO3 byproduct. Here, we present a preparation of pure CaAl-LDHs which are readily free of contamination by CaCO3. The CaAl-LDHs were prepared via a scalable method of separate nucleation and aging steps (SNAS) by facile introduction of a mixed ethanol/water media. The application of the as-prepared CaAl-LDHs was investigated as a hardening accelerator in concrete. Standard tests of the compressive and flexural strengths of the cement mortars showed that specimens containing CaAl-LDHs as a hardening accelerator exhibited a greatly enhanced performance in respect of early compressive strength and early flexural strength; and the values increased by 61% and 71%, respectively compared to the pristine concrete specimen. The enhanced performances were addressed in terms of the results in situ X-ray diffraction, scanning electron microscopy, and mercury intrusion porosimetry. Crown Copyright (C) 2009 Published by Elsevier B.V. All rights reserved.