The crystal of [Co(H2O)6]·(Hnip)2·(H2nip)2·(DMA)2·(H2O)8 has been cultured using direct method and characterized by X-ray single crystal diffractometry, elemental analysis and FTIR spectroscopy. It crystallizes in triclinic system, P-1 space group with the cell parameters of a=0.7012(1) nm, b=1.1378(2) nm, c=1.6612(3) nm, α=84.92(3)°, β=85.19(3)°, γ=85.91(3)°, V= 1.3128(5) nm3, Z= 1, Dc= 1.573 g·cm-3. Final R indices [I>2σ(I)] are:R1 =0.0279, wR2=0.0765 while R indices for all data are: R1=0.0327, wR2=0.0806. The Co coordination octahedra are each surrounded by two Hnip, two H2nip, two DMA and eight water molecules that are linked by hydrogen bonds and π-π stacking interactions. Thermal analyses of DSC and TG-DTG have been performed on the complex to predict its thermal decomposition mechanism and determine the most probable kinetic model function using Kissinger, Ozawa, integral and differential methods.