This paper aims to increase understanding of the methodological issues involved in adding biomeasures to social research by investigating the potential of an event-triggered, self-collection technique for monitoring biological response to social events. We use data from the Relationship Dynamics and Social Life (RDSL) study, which collected saliva samples triggered by a life event important to the aims of the study—the end of a romantic relationship. Our investigation found little evidence that those who complied in the biosample collection were different from those who did not comply in terms of key study measures and sociodemographic characteristics. We also found no evidence that the biosample collection had adverse consequences for subsequent panel participation. We did find that prior cooperation in the study was an important predictor of biosample cooperation, which is important information in developing biosample collection strategies. As demand for biological samples directly linked to social data continues to grow, effective low-cost collection methods will become increasingly valuable. The evidence here indicates that self-collected biosamples may offer tremendous potential to meet this demand.