If you are talking about the system portion of a library list, do a DSPSYSVAL QSYSLIBL. To see the user portion of a library list do a DSPSYSVAL QUSRLIBL. If a job description has a value of *SYSVAL under initial library list, when a job is submitted to this job description with INLLIBL(*JOBD) the resulting library list for the job will have the libraries in QSYSLIBL followed by the libraries in QUSRLIBL.
There are no libraries in “*SYSVAL”. Libraries are listed in a library list.
What “*SYSVAL” means is to look in the “system value” that is appropriate for wherever you see “*SYSVAL”. If you see “*SYSVAL” in the INLLIBL() attribute of a job description, it means to look in the QUSRLIBL system value.
Where are you seeing “*SYSVAL”? Depending on where you see it, the answer may be different.