With the emergence of phenomena like computer supported cooperative work, and especially with user-generated content and Web 2.0, new opportunities for SMEs occurred in order to collaborate on an employees’ level. As claimed by open innovation researchers, a heterogeneous group of (external) users can increase a firm’s innovative performance. These external users can be found in the form of employees of other firms participating in a SME network. However, especially SMEs are influenced by the founder’s personality and his practiced level of control, both in an offline and in an online world. Using a multi-method approach, we focus on CEOs’ perceptions of the potentials and pitfalls of Web 2.0 usage for business collaboration among employees of different firms. By providing evidence with a focus on competitive and non-competitive business collaboration mediated by Web 2.0 technologies this research may be considered an important basis for further research in employee creativity, idea generation and open innovation.