This study examined the effects of liquid and solid additives on the morphological, mechanical and thermal insulating properties of rigid polyurethane foams (PUFs). The PUFs synthesized with tetramethylsilane (TEMS) as a liquid-type additive showed a smaller average cell size and lower thermal conductivity than those with the aerosil 200 and clay 30B as solid-type additives. When TEMS was added, the average cell size of the PUF became more uniform and finer due to the reduced surface tension of the polymer solution, which increased the nucleation rate and number of bubbles produced and reduced cell size. The PUFs with TEMS showed the highest closed cell contents among the PUFs prepared using TEMS, aerosil 200 and clay 30B. This suggests that the insulation properties of PUF can be determined by both the size of the cell structure and the amount of closed cell contents in the system. The compression and flexural strengths of the PUF increased slightly when the aerosil 200, clay 30B and TEMS were added compared those of the neat PUF. The reaction profiles of the PUFs showed a similar gel and tack tree time with the reaction time among the PUFs synthesized with three different additives and neat PUF. This suggests that the nucleating additives used in this study do not affect the bubble growth of the chemical reaction, and the additives may act as nucleating agents during the formation of PUF. From the above results of the cell size, thermal conductivity, closed cell contents and reaction profile of the PUFs, liquid-type nucleating agent, such as TEMS, is more effective in decreasing the thermal conductivity of the PUF than solid-type nucleating agent, such as aerosil 200 and clay 30B.