The decomposition behaviours of composites made of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and sisal were assessed in terms of thermal stability and decomposition kinetics, under inert and oxidative conditions, by means of multi-rate linear non-isothermal thermogravimetric experiments. A statistical design of experiments was applied to study the influence of the addition of sisal (0-10-20-30%wt), the presence coupling agent (Yes/No) and the applied conditions of work (inert or oxidative). An improvement of the thermal and thermo-oxidative stability of PHBV with the addition of sisal was observed for all cases. An accurate methodology based on iso-conversional methods was applied to simulate the potential of thermal recovery technologies, such as pyrolysis and controlled combustion, to use these biocomposites after the end of their service life. The mathematical descriptions of both thermo-chemical reactions were helpful in the evaluation of the eventual optimal operational conditions to carry out a suitable energetic valorisation. A minimum of 240°C and 137 kJ/mol of activation energy in inert conditions and 236°C and 118 kJ/mol in oxidative conditions ensured the feasibility of the reactions regardless the composition of the PHBV/sisal biocomposites, which may ease the operability of further energy valorisation with the aim to turn biowaste into new fuels.