A study of the effects of MWCNT as a nucleating agent on the formation reactions of the rigid polyurethane foams (RPUFs) was carried out. Sample PUFs, formulated with grease-type master batch of MWCNT/surfactant, were fabricated by free-rising method. Temperature changes with time during foaming process were measured using a digital thermometer. RPUF foaming process was observed to undergo 2-step processes with temperature inflection around 60 sec after the start of reaction, and then reached slowly the max. temperature. While the max. temperature of neat PUF was measured as ca. 120oC, that of the samples with MWCNT were as higher value as ca. 130oC, and, even the time to reach that temperature was reduced by about 15 sec. Average cell size of PUF samples decreased from 185.1 for the neat PUF to 162.9 μm for the sample of 0.01 phr of MWCNT. As the result, it was considered that MWCNT in RPUF foaming process could play a roll both as a nucleating agent and as a catalyst.