Abstract Tars and alkali ashes from biomass gasification processes currently constitute one of the major problems in biomass valorisation, generating clogging of filters and issues related with the purity of syngas production. To date, these waste residues find no useful applications and they are generally disposed upon generation in the gasification process. A detailed analysis of these residues pointed out the presence of high quantities of Ca (>30 wt%). TG experiments indicated that a treatment under air at moderate temperatures (400–800°C) decomposed the majority of carbon species, while XRD indicated the presence of a crystalline CaO phase. CaO enriched valorized materials turned out to be good heterogeneous catalysts for biodiesel production from vegetable oils, providing moderate to good activities (50%–70% after 12 h) to fatty acid methyl esters in the transesterification of sunflower oil with methanol.