Research on sustainable people management has focused on the macro level, while overlooking methods to implement sustainability at the operational level, specifically, in its employee hiring processes. We argue that when hiring processes assess applicants’ sustainability values and behaviors, they determine the degree of values alignment or person-organization (PO) fit between the applicant and the organization. Thus, they result in the strategic hiring of individuals who will support the organization’s sustainability efforts. We focus on how sustainable organizations can use structured behavioral interviews to assess P-O fit. First, we interviewed 10 hiring managers about the role of P-O fit in their hiring processes and their methods for assessing this alignment. We found that managers described using behavioral interviews to assess applicants’ fit with organizational sustainability values. However, while significant evidence supports the idea that a structured interview process is essential to obtain reliable and valid information about job candidates, the majority followed an unstructured interview format. Second, we explored how managers can overcome some of the limitations associated with this approach by drawing from established measures and studies, including the General Ecological Behavior (GEB) scale (Kaiser, 1998) and the Sustainability Mindset Indicator (Rimanoczy & Klingenberg, 2021). We present recommendations for incorporating the former as an assessment test and the latter within a structured interview format.