Callum Wheeler, of Aylesham, is scheduled to appear at Medway Magistrates Court on Tuesday via video conference.
Mrs. James was found dead in Akholt Wood near her home in Snowdown on April 27.
The PCSO, 53, suffered serious head injuries while walking his dog Toby, who was found unharmed by his side.
Kent Police arrested Wheeler on Friday evening.
The force had been granted a 36-hour extension to continue to keep him in detention, which lasted until Monday evening.
The National Crime Agency supports the Kent Police investigation into Ms James’ murder, adding that they have pledged to “seek justice for Julia”.
Crimestoppers have offered a reward of up to £ 10,000 for information leading to the conviction of their killer.
Police last week released an image of Ms James in the clothes she wore before she was killed.
The photo showed her in a light blue waterproof coat, blue jeans and dark brown Wellington-style boots, as she walked with her Jack Russell.
Police said it was the same clothes, other than gloves, that she wore on the day she died.