This chapter provides a summarized and objective review over the relationships among innovation, social innovation, entrepreneurship, social entrepreneurship, new business models (NBM), and product (good, service, idea) value and sustainability (economic, social, ecological, and psychological). A study has been done in Porto region through interviews with 13 social innovators and entrepreneurs, in order to evaluate those relationship. The conceptual base for analysis is the theories developed by Jonker (2012) and Carvalho and Jonker (2015). It has been concluded that market-oriented social innovation has a crucial role in the development social entrepreneurship. Moreover, these NBM should be adjusted to population needs towards societal well-being, by combining creation of shared value, co-creation of value, and multiple value creation. Thus, the value set (social innovation) contributes to economic, social, ecological, and psychological sustainability, and consequently to human, social and territorial development.