Effects of Li-addition on the formation process of Bi-2212 phase have been studied for samples with a nominal composition of Bi:Sr:Ca:Cu:Li=2:1.5:1.5:2:0.2. Samples were heated at temperatures ranging between 560°C and 730°C in air with various heating rates. The formation range of the phases formed was determined by powder X-ray diffraction method(XRD). Li-addition seems to bring two different effects on the formation process of the Bi-2212 phase: an acceleration of the formation of Bi-2201 phase on heating and early stage of holding at 730°C, and a promotion of phase transformation of Bi-2201 phase to Bi-2212 phase after holding for a few hours. Such two effects can be explained by formation of two different oxides which were newly found. The microstructures of the newly found oxides were observed by scanning electron microscopy(SEM), high-resolution transmission electron microscopy(HR-TEM) and electron diffraction(ED).