Abstract Utilisation of solar energy for thermochemical conversion of biomass can facilitate sustainable development of society by reducing greenhouse gas (GHG) emissions which originate from excessive use of conventional sources of energy. In this work, gas and liquid fuels obtained from solar assisted pyrolysis of chicken-litter waste were upgraded using CaO and char catalysts. The catalysts were loaded in the solar reactor in in-situ and ex-situ modes at different catalyst to biomass ratios. In both cases there was substantial decrease in CO2 accompanied by an increase in the formation of CO and H2 with temperature and catalyst to biomass ratio. The in-situ pyrolysis with 50% CaO loading exhibited maximum CO (63 wt%) and H2 (15 wt%) yields at 800 °C. Similarly, the in-situ pyrolysis with 50% char catalyst produced 60 wt% CO and 5 wt% H2. The addition of CaO exhibited considerable deoxygenation performance for the fatty acids. Minimum concentrations of fatty acids in the liquid product achieved with 50% CaO in the in-situ and ex-situ pyrolysis were 8% and 3%, respectively. On the other hand, the addition of char did not show significant deoxygenation difference for either the alcohols or fatty acids of the bio-oil compounds.