The experienced defender joined the Reds from Doncaster Rovers Belles after skippering her former club to the FA WSL2 title last term.
Meanwhile, England defender Sophie Bradley-Auckland has been named team captain by Women’s manager Neil Redfearn.
On the appointment of Little as club captain, Redfearn said: "Leandra is going to be a massive influence for us both on and off the pitch this season.
"She showed what a real leader she was during Doncaster Rovers Belles' title success last season and will prove to be a crucial member of the squad this year for Liverpool Women.