With the development of the network economy, especially the promotion and popularization of mobile networks, traditional offline businesses are further integrated with online businesses, promoting the development of business online strategies. However, with the growth of enterprises’ business, their negative externalities on the environment have gradually become prominent, further affecting sustainable consumption. The relationships between businesses, the environment, and consumption have become the focus of attention. China’s fast-growing bottled water companies face similar challenges. The pollution that occurs due to bottled water packaging poses great threats to consumers. Hence, this study extended the Theory of Planned Behavior (TPB) by integrating three risk aspects, namely, water pollution risk perception (WPRP), non-degradable package pollution risk perception (NPPRP), and false information risk perception (FIRP), to examine the consumers’ perceptions toward these risk aspects before purchasing bottled water online. This study employed a cross-sectional approach to collect data from online consumers via a survey method. A total of 401 valid samples were collected and then analyzed via a structural equation model using the AMOS statistical package. The results showed that attitude (AT), subjective norm (SN), and perceived behavior control (PBC) toward online bottled water purchase had significant and positive effects on the consumers’ purchase intentions (PIs). However, under the influence of risk perception, the consumers’ attitudes, SNs and PBC became suppressed by WPRP, and SN became suppressed due to the impact of FIRP. Furthermore, the negative impacts of NPPRP and FIRP on PI were partially mediated by AT, SN and PBC. Meanwhile, WPRP imposed the most significant direct effect on PI. The study results will help businesses to develop better online strategies to reduce the risk perception of bottled water and provide theoretical value and practical guidance for realizing sustainable consumption.