Fundamental physical chemical properties of monolayers formed from a new anionic gemini surfactant with a minimal-length (single-bond) spacer unit have been investigated at the air-water interface and compared with those of monolayers formed from affiliated comparator surfactants. The minimal spacer surfactant, dubbed C18-0-C18, exhibited strikingly different packing characteristics from an anionic gemini surfactant with a comparatively bulkier headgroup, including the formation of close-packed, crystalline films, and shared similar characteristics to simple fatty acid-based monolayers. Monolayers of C18-0-C18 also exhibited good stability at the air-water interface and transferred with reasonable efficiency to solid substrates, although the film integrity was compromised during the transfer. Results from this work suggest that the single-bond spacer approach might be more broadly useful for designing gemini surfactants that pack efficiently into ordered monolayers.