Prof Zollo at MIT worked with a group of scientists to analyse differences between entrepreneurs and manager’s brains. Turns out some parts of the brain is wired differently. More from their site [Also read my earlier post on Amateurs vs Professionals ]

In our study, we used an fMRI to map brain activity in 25 entrepreneurs and managers while they performed simple tasks that replicated what we call exploitation and exploration type of settlement loans. Exploitation tasks are ones associated with finding new ways to optimize the performance of current tasks based on refinements of existing practices. Explorative tasks are ones involving disengagement from the current task to search for alternative courses of action and new things to do to achieve overarching goals, rather than doing current things better. In those processes, individuals need to forgo immediate gratification and engage in experimentation with untried approaches.
We found that when entrepreneurs performed explorative tasks, they used both the left and right sides of the frontal parts of their brains, the entire so-called pre-frontal cortex. In comparison, managers tended to use primarily the left sides of the frontal part of their brains. This is an important difference, as the right side of the pre-frontal cortex is associated with creative functions involving high-level thinking (like poetry, arts, etc.), whereas the left side is associated with rational decision-making and logical thinking. So, in a way, we found that entrepreneurs seem to be capable of using the entirety of their high-level thinking capacities (“executive functions”), while managers were more narrowly focused on rational and logical reasoning.
This doesn’t mean entrepreneurs are smarter or even that they explore more than managers. But when they do explore, they use their brains in a more complete way.
This might explain the capacity of entrepreneurs to take more risks given their ability to reason with both the rational and emotional/creative parts of their brains. However, it also raises the interesting question of nature versus nurture. Do entrepreneurs’ brains work differently as a result of their work experiences, which might have conditioned their brains in a certain way? Or were they born this way and consequently self-select to undertake entrepreneurial careers?