We assessed the impact of an individual difference variable, relationship-focused thinking, on women's acute salivary cortisol responses during and after a guided imagery task. Specifically, 29 healthy women, all of whom were experiencing high levels of passionate love, but varied on levels of relationship-focused thinking, were assigned to one of two experimental conditions: a partner reflection condition or a cross-sex friend reflection condition. Results indicated that women experiencing passionate love evidenced increased cortisol levels when asked to reflect on their romantic partner and relationship relative to women asked to reflect on a cross-sex friendship, but this difference was particularly pronounced and relatively long-lasting for those women characterized by a high amount of relationship-focused thinking. Our study significantly expands extant work on the passionate love-cortisol link by isolating the impact of a specific psychological variable, relationship-focused thinking, on the physiological experience of falling in love. We believe our work highlights the advances that can be made when established work in the close relationships and neuroendocrine fields are integrated.