If the OUPV and 100 GRT Master are for the same route (e.g. near coastal or inland), you don’t actually get the OUPV endorsement on your MMC - only the Master. The Master endorsement covers you for OUPV. But it doesn’t hurt to put both on your application.
§ 15.905 Uninspected passenger vessels.
(a) An individual holding a license or MMC endorsed as master or pilot of an inspected self-propelled vessel is authorized to serve as operator of an uninspected passenger vessel of less than 100 GRT within any restrictions, other than tonnage limitations, on the individual’s license or MMC.