Some studies provide evidence that humans could actively exploit the alleged technological advantages of autonomous vehicles (AVs). This implies that humans may tend to interact differently with AVs as compared to human driven vehicles (HVs) with the knowledge that AVs are programmed to be risk-averse. Hence, it is important to investigate how humans interact with AVs in complex traffic situations. Here, we investigated whether participants would value interactions with AVs differently compared to HVs, and if these differences can be characterized on the behavioral and brain-level. We presented participants with a cover story while recording whole-head brain activity using fNIRS that they were driving under time pressure through urban traffic in the presence of other HVs and AVs. Moreover, the AVs were programmed defensively to avoid collisions and had faster braking reaction times than HVs. Participants would receive a monetary reward if they managed to finish the driving block within a given time-limit without risky driving maneuvers. During the drive, participants were repeatedly confronted with left-lane turning situations at unsignalized intersections. They had to stop and find a gap to turn in front of an oncoming stream of vehicles consisting of HVs and AVs. While the behavioral results did not show any significant difference between the safety margin used during the turning maneuvers with respect to AVs or HVs, participants tended to be more certain in their decision-making process while turning in front of AVs as reflected by the smaller variance in the gap size acceptance as compared to HVs. Importantly, using a multivariate logistic regression approach, we were able to predict whether the participants decided to turn in front of HVs or AVs from whole-head fNIRS in the decision-making phase for every participant (mean accuracy = 67.2%, SD = 5%). Channel-wise univariate fNIRS analysis revealed increased brain activation differences for turning in front of AVs compared to HVs in brain areas that represent the valuation of actions taken during decision-making. The insights provided here may be useful for the development of control systems to assess interactions in future mixed traffic environments involving AVs and HVs.