The `Tourist- actress - who raises six children Maddox, nine, Pax, seven, Zahara, six, Shiloh, four and two-year-old twins Knox and Vivienne with actor Brad Pitt - has reportedly signed a high profile, print-only deal with the French brand.
According to E! News, the deal would see Angelina earn "close to $6 million" for the modelling contract.
The 35-year-old beauty - who has recently launched a jewellery line - would be following in the footsteps of Madonna and Jennifer Lopez, who have both modelled for LouisVuitton in the past.
Angelina has previously revealed she loves letting her children dress however they want, and defended her daughter Shiloh who is often pictured wearing boy`s clothes.
She said: "Children should be allowed to express themselves in whatever way they wish without anybody judging them because it is an important part of their growth.
"I think Shiloh is fascinating, the choices she is making. And I would never be the kind of parent to force somebody to be something they are not. I think that is just bad parenting."