Thermal behaviour of newly synthesized niobium(V) aryloxides of composition [NbCl5−n(OC6H4CH(CH3)2-4)n] (where n = 1 → 5) synthesized by the reactions of niobium pentachloride with 4-isopropylphenol in predetermined molar ratios in carbon tetrachloride has been studied by thermogravimetric (TG) and differential thermal analysis (DTA) techniques. The results showed that thermal decomposition of complex of composition [NbCl4(OC6H4CH(CH3)2-4)] resulted in the formation of NbOCl3 as the ultimate decompositional product while all other complexes yielded Nb2O5 as the final product of thermal decomposition. From the mathematical analysis of TG data, the kinetic and thermodynamic parameters viz. energy of activation, frequency factor, entropy of activation, etc. have been evaluated using Coats–Redfern equation.