hi,
you can do it , but you need to take into considerations , since /home gets installed as part of the OS install , if you do an upgrade would it require /home to be in rootvg
my guess is not , also try mksysb
Steps you would take , since you will be moving /home
to a new volume group, :-
1. Create your new volume group
2. backup /home
3. umount /home
4. remove /home :- rmfs /home
5. Create /home in new volume group
6. restore /home
HTH