In the current study, sugarcane bagasse-derived biochar catalysts were synthesized by doping with metal-free heteroatoms including nitrogen, phosphorus, oxygen, and boron and their efficacy was tested for catalytic co-pyrolysis of walnut shells (WS) and palm oil fatty acid distillate (PFAD) using Py-GC/MS. The biochar catalysts’ properties and their effectiveness on co-pyrolytic bio-oil (overall product distribution, selectivity towards aliphatic and aromatic hydrocarbons, and carbon number ranges) were extensively examined. Among the various catalysts considered, boron-doped biochar (BCB) demonstrated effective performance due to an improved surface area, porosity, and acidity and resulted in a significantly increased hydrocarbon yield, particularly in the gasoline and diesel range, and preference for aromatic over aliphatic hydrocarbons. The optimum bio-oil quality was achieved at a feedstock-to-catalyst ratio of 2:1 and a pyrolysis temperature of 750 °C, with a hydrocarbon yield of 90.8 % and aromatic hydrocarbon selectivity of 63.5 %. Overall, the study underscores the role of BCB in fostering deoxygenation, decarboxylation, and aromatic selectivity via thermal and catalytic pathways, highlighting the potential of non-metallic doped biochars for bio-oil upgrading.