The development of thermal conductivity reference materials for high-temperature insulation consists of three stages: provisional assessment of candidate reference materials, detailed assessment of candidate reference material(s) and corresponding inter-laboratory comparisons. This paper describes the detailed characterization of a candidate high-temperature thermal conductivity reference material, a high-density calcium silicate (HDCaSi-N). The selection criteria, assessments of uniformity and stability, the thermal expansion behavior and their effects on the thermal conductivity reference specimens are presented in the paper. The uniformity assessments include the thermal expansion variation in orthogonal orientations and different locations and from different boards, as well as thermal conductivity variation within the batch of the specimens. The dimensional stability assessment in terms of thermal expansion and the short-term stability in terms of thermal conductivity are also presented.