Upgrading VMFS datastores and SDRS | frankdenneman.nl:

vSphere 5 offers a pain free upgrade path from VMFS-3 to VMFS-5. The upgrade is an online and non-disruptive operation which allows the resident virtual machines to continue to run on the datastore.

“Painless”, unless…

If the VMFS-3 datastore is formatted with a larger blocksize than 1 MB, it may be better to empty the VMFS datastore and reformat the LUN with a fresh coat of VMFS-5 file system. The effort and time put into the migration will have a positive effect on the performance of the daily operations of Storage DRS.