In this field guide, we outline empirical and theory-based approaches to characterize the fundamental properties of liquid multivalent-ion battery electrolytes, including (i) structure and chemistry, (ii) transport, and (iii) electrochemical properties. When detailed molecular-scale understanding of the multivalent electrolyte behavior is insufficient we use examples from well-studied lithium-ion electrolytes. In recognition that coupling empirical and theory-based techniques is highly effective, but often nontrivial, we also highlight recent electrolyte characterization efforts that uncover a more comprehensive and nuanced understanding of the underlying structures, processes, and reactions that drive performance and system-level behavior. We hope the insights from these discussions will guide the design of future electrolyte studies, accelerate development of next-generation multivalent-ion batteries through coupling of modeling with experiments, and help to avoid pitfalls and ensure reproducibility of modeling results.