Libon is a first class municipality with a land area of . It is about west-north-west of the provincial capital of Albay Legazpi City, and about east-south-east of Manila. It is classified as a partly urban municipality with 47 barangays subdivided into seven leagues: St. James (Poblacion), Lakeside (barangays within the vicinity of Bato Lake), Coastal (barangays located along the Albay West Coast), Big Five (barangays abundant in rice, corn, and vegetables), Interior Nine (hinterland barangays forefront in vegetable production and livestock raising), Palayan (barangays foremost in rice production), and Six Hills (barangays concentrated to coconut production).