Over the years, the overconsumption of natural resources has been an issue of concern. Companies have been inducing sustainable practices and approaches to help the environment. By specifically applying the sustainability theory of planned behavior, this study sought to extensively investigate behavioral preference and intention to buy green and sustainable products across name-brand businesses in a developing country. Utilizing Structural Equation Modeling, this study examined responses from 300 valid participants. The results revealed that consumers’ purchasing preferences and intentions are affected by customer expectation for the products, by the government, and by customer concern for the environment. It was seen that customers are prepared to pay extra for name-brand stores that sell eco-friendly or sustainable goods. In accordance, consumers’ purchase intentions are greatly affected by the customer preference or expectation for a product, as the findings indicate that customer-perceived value has the highest influential and consequential relationship to behavioral purposes. Customers are inclined to purchase eco-friendly goods if the sustainable product meets the requirements and expectations of the consumer. Furthermore, consumers’ purchasing intentions in buying green products from name-brand shops are also affected by the government, individuals’ environmental concerns and awareness, individuals’ personal needs and beliefs, society, and individual attitudes. For name-brand stores, consumers’ behavioral intentions to purchase environmentally friendly and sustainable goods are the most strongly associated with their perception of their own value, followed by perceived authority support and perceived environmental concern. The findings and results of this study can be relevant in understanding and exploring consumers’ behavioral intentions to purchase green products from name-brand shops.