Over the past several decades, interest in using human milk as a biomonitoring matrix has increased. However, it is not always an easy matter for a new mother to provide a milk sample. In this article, guidance on facilitating collection of human milk is provided. This includes addressing the mother's ease in expressing a milk sample, and engaging with many audiences to reduce the likelihood of negatively impacting the already low breastfeeding rates in the United States. In addition, this article covers concepts regarding long-term storage and integrity of human milk samples to maximize the utility of those samples, and proposed methods for improving public access to the full spectrum of human milk biomonitoring data, with context to understand the information presented. The environmental chemicals and chemical classes for which robust analytical methods exist are enumerated, and a process for prioritizing the development of analytical methods for additional environmental chemicals is described.