The global environmental issues on climate change and wider scope of sustainability have growing impact over the few decades on the social demand and the international political agenda. As the implementation of such policies is often hindered by the national sovereignty, some firms have adopted voluntary involvements to fulfill those issues and engage with stakeholders. From the wide standpoint of social responsibility and sustainable development, the CSR (Corporate Social Responsibility) and SRI (Social Responsibility Investment) are becoming globalised concepts and most multinational firms introduce sustainability practices to reach stakeholders' satisfaction and give a positive signal to the market. Until recently, most of studies have showed the impact of CSR and SRI on the performance in the sustainable development aspect. However, there are lots of conversely debates on the correlations between voluntary activities and financial performances as well as the resulting analyses have statistical limitations. From this, this study proposes the relationship of environmental and sustainable issues with the innovation activities and performance of firms. 806 firms are divided into specific groups according to the CDP Global 500 report and the firms list of Dow Jones Sustainability Index (DJSI) between 2008 and 2009. Using the empirical analysis, this study identifies the relation between environmental, sustainable implementations and innovative activities. Classifying the established environmental and sustainable issues as well as proposing an empirical model of the links among environmental, sustainable behaviors and innovation activities is another contribution of this study. The results show that the firms' behavior is varied depending on the industry sectors, firm characteristics, and environmental and sustainable activities. Hence, our study considering the sustainable, environmental behavior and innovation of firms can offer solution to which value for which organization.