Currently furfural production has been the subject of increased interest because it is a biobased chemical able to compete with fossil-based chemicals. Furfural is characterized by flammability, explosion, and toxicity properties. Improper handling and process design can lead to catastrophic accidents. Hence it is of most importance to use inherent safety concepts during the design stage. This work is the first to present several new downstream separation processes for furfural purification, which are designed using an optimization approach that simultaneously considers safety criteria in addition to the total annual cost and the eco-indicator 99. The proposed schemes include thermally coupled configuration, thermodynamic equivalent configuration, dividing-wall column, and a heat integrated configuration. These are compared with the traditional separation process of furfural known as the Quaker Oats Process. The results show that because of a large amount of water present in the feed, similar values are obtained for total annual cost and eco-indicator 99 in all cases. Moreover, the topology of the processes has an important role in the safety criteria. The thermodynamic equivalent configuration resulted as the safest alternative with a 40% reduction of the inherent risk with respect to the Quaker Oats Process, and thus it is the safest option to purify furfural.