The enzyme PAD from Lactobacillus plantarum CECT 748T decarboxylates some cinnamic acids namely p-coumaric acid (p-CA), caffeic acid (CA), and ferulic acid (FA) into their corresponding 4-vinyl derivatives (4-VD): 4-vinyl phenol (4-VP), 4-vinyl catechol (4-VC), and 4-vinyl guaiacol (4-VG), respectively, which are valuable food additives mainly employed as flavouring agents. The gene encoding this enzyme was cloned and overexpressed in Escherichia coli. Recombinant E. coli cells overproducing L. plantarum PAD showed a preference to degrade mainly p-CA and CA. Sterilized liquors obtained after alkaline hydrolysis of corn cob or alkaline hydrolysis of the solid residue coming from acid hydrolysis of corn cob were employed as growth media in fermentations performed in shaker or bioreactor. The fermentative process allowed converting 2222.8 mg/L p-CA into 993.9 mg/L 4-VP. The process described here allowed the production with a high-yield of a valuable food additive from a by-product of the food industry.