The ecosystem services (ES) optional capacity value (OCV) indicates the optional capacity of supporting the total value produced by human being's economic and social activities (TVPH) provided by the total volume of an ES which is indispensable to human survival. The OCV is described by the product of multiplying the TVPH by the optional capacity. The optional capacity is defined by the freedom of choosing the ES consumption from total ES volume, which is indicated by the average uncertainty of choosing the ES consumption from its total volume. The average uncertainty is described by log base 2, which indicates the uncertainty in a binary decision and is measured in bits. As combining the socio-economic index (i.e. TVPH) and the ES indexes (i.e. total ES volume and ES consumption), the OCV indicates the socio-economic conditions and the ES conditions at the same time. As the OCV describes the complementarity of development and protection, the usage of OCV in ES management will promote the endeavor for ecological civilization. However, how to introduce the OCV into management practice is still unclear. Especially, the method of how to introduce OCV into the frameworks and methods of quantifying the payments for ecosystem services (PES) and the value of natural resources (VNR) is needed to study urgently. To explore the frameworks and methods of quantifying the PES and the VNR based on the indicator of OCV, we analyzed the OCV of water resources supply in Zhujiang River Basin, China. Then, the PES between hydrologic units was discussed based on the OCV of ES spatial subsidies. The value of water resources in each hydrologic unit was quantified using the OCV of water resources supply. The results showed that the OCV of water resources supply of the hydrologic unit was supplied mostly (nearly 74%) by the subsidies from upstream hydrologic units. The value of water resources in each hydrologic unit (except the Zhujiang Delta) was more or less affected by the socio-economic conditions in downstream hydrologic units. We discussed the framework of the PES along with the principles of (1) interests sharing and responsibilities bearing, and (2) equal pay for equal work and based on the OCV of water resources supply of passing-by water. We also discussed the framework of water resources value quantification based on the OCV of water resources supply in our case study. It is obvious that these two frameworks based on the OCV will coordinate the development between hydrologic units and promote the watershed ecological civilization of Zhujiang River Basin.