The company said 228 jobs will go as a result of the separation, with cuts in IT, administration, buying and ethical trading departments.
"We are hopeful that the majority of redundancies will be achieved voluntarily," a Littlewoods spokesman said. "Having looked at our requirements, we decided that this 'right sizing' was the right move."
The spokesman said the 66 job cuts in IT - about 20% of the department - would not have any immediate impact on IT projects, although he was unable to comment on the long-term implications.
The Union of Distributive and Allied Shop Workers said it is holding meetings to negotiate redundancy terms.