On December 7, 2009 Pickering was involved in a fight with the coach of a youth soccer team that had just finished playing against his son's team.
Pickering and his former wife Leisha have five sons, Will, Ross, Jackson, Asher, and Harper. Chip announced in June 2008 that he filed for divorce from Leisha in Madison County, Mississippi, citing irreconcilable differences. On July 16, 2009 it was announced that Leisha had filed an alienation of affection lawsuit against Elizabeth Creekmore Byrd, a woman with whom Chip allegedly had an affair. The lawsuit claimed that the adulterous relationship ruined the Pickerings' marriage and his political career. In a column on July 24, 2009 , Cokie and Steve Roberts wrote about the Washington, DC, Fellowship Foundation at 133 C Street South East, where the trysts allegedly took place. Leisha Pickering, they wrote, "claims that instead of praying, another woman was preying on her husband" there. Roberts and Roberts indicated that Leisha was further motivated to pursue the divorce because her ex-husband's paramour "made Pickering quit Congress just when he might have been appointed to the Senate. We would be surprised if ex-wives have some legal recourse for disappointment over a Senate seat, but hey, Leisha Pickering's going for it."