Genesis 13:18 describes Abraham settling near the oaks of Mamre at Hebron and building an altar to the Lord. After Sarah died, Genesis 23 records Abraham purchasing the cave of Machpelah from Ephron the Hittite as a permanent burial possession.
The spies sent by Moses reached Hebron during their exploration of Canaan. Joshua later captured the city, which became part of Judah's territory and was assigned as a Levitical city and city of refuge.
Hebron became politically crucial after Saul's death. David settled there and was anointed king over Judah. Seven and a half years later representatives of all Israel came to Hebron and anointed him king over the united tribes before he moved his capital to Jerusalem.