Synchronous chat reference services have emerged as viable alternatives to the traditional face-to-face (FtF) library reference encounter. Research in virtual reference service (VRS) and client-librarian behavior is just beginning with a primary focus on task issues of accuracy and efficiency. This study is among the first to apply communication theory to an exploration of relational (socioemotional) aspects of VRS. It reports results from a pilot study that analyzed 44 transcripts nominated for the LSSI Samuel Swett Green Award (Library Systems and Services, Germantown, MD) for Exemplary Virtual Reference followed by an analysis of 245 randomly selected anonymous transcripts from Maryland AskUsNow! statewide chat reference service. Transcripts underwent in-depth qualitative content analysis. Results revealed that interpersonal skills important to FtF reference success are present (although modified) in VRS. These include techniques for rapport building, compensation for lack of nonverbal cues, strategies for relationship development, evidence of deference and respect, facesaving tactics, greeting and closing rituals. Results also identified interpersonal communication dynamics present in the chat reference environment, differences in client versus librarian patterns, and compensation strategies for lack of nonverbal communication.