Solid adducts SbX3.L-pic (X=Cl, I and L=alpha-, beta- and gamma-picolines) were synthesized and characterized by elemental analysis, H-1 and C-13 NMR, IR spectroscopy and thermal analysis. ne infrared spectroscopy and the magnetic resonance for H-1 and C-13 nuclei of these compounds suggest that the ligands coordinate through nitrogen atom. Kinetic studies were accomplished by means of thermogravimetric data, through isothermal and non-isothermal techniques. The best adjusting models for adducts thermal decomposition were R-1 for isothermal and R-1 and R-2 for the non-isothermal methods. The energy of activation values obtained by isothermal method indicate the following orders of thermal stability for adducts: i) SbCl3.alpha-pic>SbCl3.beta-pic>SbCl3.gamma-pic and ii) SbI3.beta-pic<SbI3&BULL;&gamma;-pic<SbI3.alpha-pic. The activation energy values obtained by non-isothermal were higher than those from isothermal methods, showing the order of stability: iii) SbCl3.alpha-pic<SbCl3&BULL;&beta;-pic<SbCl3.gamma-pic and iv) SbI3.beta-pic<SbI3&BULL;&alpha;-pic&CONG;SbI3&BULL;&gamma;-pic. These obtained data through R, model presented the kinetic compensation effect for trichloride adducts, which could be associated to both isothermal and non-isothermal processes.753975988