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This paper sheds light on the questions, Why does knowledge spill over? and How does knowledge spill over? The answer to these questions we suggest lies in the incentives confronting scientists to appropriate the expected value of their knowledge considered in the context of their path-dependent career trajectories. In particular, we focus on the ability of scientists to appropriate the value of knowledge embedded in their human capital along with the incentive structure influencing if and how scientists choose to commercialize their knowledge. We conclude that the spillover of knowledge from the source creating it, such as a university, research institute, or industrial corporation, to a new-firm startup facilitates the appropriation of knowledge for the individual scientist(s) but not necessarily for the organization creating that new knowledge in the first place.