The reality TV star-turned-trainee lawyer hopes to use her legal connections to secure C-Murder's freedom.
He was handed a life sentence in 2003 after he was found guilty of the 2002 killing of 16-year-old Steve Thomas in a New Orleans, Louisiana nightclub.
The conviction for second degree murder was overturned in 2006, only for C-Murder, real name Corey Miller, to be convicted again and given the same sentence following a second trial in 2009.
He has always maintained his innocence and has continued to fight for justice, but his latest request for a retrial was shot down last year, despite two men, who appeared as witnesses for the prosecution in the original case, confessing to lying under oath after reportedly being cornered by police detectives.
Longrunning rumours have also indicated jurors were pressured into convicting Miller.
Kim has joined forces with C-Murder's ex, R&B singer Monica, as part of her ongoing fight for criminal justice reform, and although Master P welcomes the media attention the pair will bring to the case, he wants them to brace for a tough fight, suggesting local politics and corruption are partly to blame for his brother's incarceration.
"My whole thing is getting my brother home, and so whatever anybody can do, I appreciate it...," Master P tells TMZ.
"It's just a blessing that people are understanding that my brother is innocent. He should've been free (sic)...".
However, he explains his family has "spent millions of dollars" fighting for C-Murder's freedom, and it's done little to change the situation in Louisiana.
"This place has a lot of corruption...," he warns. "Hopefully Kim K, her celebrity status now (will help), but this is not going to be easy."
Meanwhile, C-Murder has managed to share his joy at the news on Instagram, calling the pair God's "angels".