The pervasive post-adoption of on-demand software-as-a-service (SaaS) products via the Internet has provided clients with sufficient convenience and functional flexibility to rent and build the multifunctional services they require. Prior research has called for a deeper understanding of how client firms encourage the exploration of SaaS applications in the workplace. However, exploring the best service combinations depends on the clients’ socially related motivation. Hence, we draw on social capital theory in this study to examine clients’ intentions to explore new SaaS service features. We use service quality to complement structural capital as an indicator, as it is more suitable for assessing the service structure of systems. Drawing on a sample of 246 employees in the IT service departments of small- and medium-sized companies in Taiwan, we generate the following empirical results. First, most of the main effect paths only show significant positive signs for the effect of relational capital on the intention to explore, and the effect of environmental quality on social capital is not supported. Second, we rebuild the mediation model to test the non-supported hypotheses and find that relational capital partially mediates the relationship between service quality and the intention to explore. The theoretical and practical implications of these findings are discussed.