Calcium carbonate whisker (CW) can work as a cost-effective and environment friendly micro-fiber in reinforcing cementitious composites. Influence of high temperature on micro-structure of CW reinforced cement paste by nanoindentation and mercury intrusion porosimetry test are studied in this research. Up to 500 °C, the indentation depth, elasticity modulus, indentation hardness and interfacial transition zone width of CW reinforced cement paste are near or even better than that at room temperature, due to the coupling effect of CW transformation from aragonite to calcite and internal autoclaving. However, when the temperature is higher than 700 °C, nano-mechanical properties of CW reinforced cement paste degenerated significantly, due to the decomposition of CW and hydration products. Similarly, with the increase of temperature up to 400 °C, the porosity and pore size increase little or even decrease, while the fractal dimension of pore volume increases. With the introduction of CW, the pore parameters and fractal dimension are decreased up to 400 °C, due to the filler effect of CW. When the temperature is higher than 700 °C, the pore diameter and fractal dimension of CW reinforced cement paste are significant higher than that of pure cement paste, due to the decomposition of CW and hydration products. In CW reinforced cement paste, the fractal dimension was increased with the increased temperature and porosity in this research. There are negative correlations between the pore volume fractal dimensions and the strengths of CW reinforced cement paste. Fractal dimension is a useful tool to evaluate the change of pore structure at high temperature.