Ferroelectric domain orientations have been mapped using piezo-force microscopy, allowing the calculation and statistical analysis of interfacial polarization angles, the head-to-tail or head-to-head configuration, and any cross-coupling terms. Within 1 µm2 of an epitaxial (001)p-oriented BiFeO3 film, there are >40 µm of linear domain boundary based on over 500 interfaces. 71° domain walls dominate the interfacial polarization angles, with a 2:1 preference for uncharged head-to-tail versus charged head-to-head boundary types. This mapping technique offers a unique perspective on domain boundary distributions, important for ferroelectric and multiferroic applications where domain wall parameters are critical.