Photharam was a district (khwaeng) of Mueang Ratchaburi in the 19th century. In 1836 the district office was relocated from the mouth of Bang Tanod canal to the east bank of the Mae Klong River opposite Wat Chaloem Art. On 10 March 1952 it was moved to its present location in the municipality of Photharam.
The district is divided into 19 sub-districts (tambons), which are further subdivided into 156 villages (mubans). There are six municipal (thesaban) areas. The town (thesaban mueang) Photharam covers tambon Photaram. The townships (thesaban tambon) Ban Lueak, Ban Sing, and Chet Samian each cover the same-named tambons completely. The township Khao Khuang covers tambon Nang Kaeo and parts of Chamrae, Tao Pun, and Khao Cha-ngum. Township Nong Pho covers parts of tambon Nong Pho. There are a further 14 tambon administrative organizations (TAO).