The crystallography and chemistry of interfaces between austenite and ferrite in duplex steels control many important materials properties but remain poorly understood. In this study, we experimentally show that in an additively manufactured and heat treated duplex stainless steel, the majority of austenite-ferrite interfaces terminate on {111}A/{110}F planes, and this behaviour is more pronounced for rational interfaces with the Kurdjomov-Sachs orientation relationship. Interface segregation was found to be controlled by not only the interface crystallography but also the bonding properties of solute atoms. Solute elements showed higher interfacial excess at irrational interfaces. Furthermore, a heterogeneous distribution of selected solute elements in austenite-ferrite interfaces planes was observed. Our findings reinforce the importance and, in fact, necessity to consider five independent crystallographic parameters and chemical architecture of interphase boundaries for advanced control of mechanical and other critical properties in duplex materials.