Refractory Metal Intermetallic Composites (RMICs) based on the Nb-Si system are considered as candidates of next-generation high temperature materials (i.e. >1200°C). Ti and Cr have been shown to have beneficial effects on the oxidation resistance and mechanical properties of Nb-Si alloys. Phase equilibria in the Nb-Si-Ti system have been studied in detail. The present study has investigated multiphase equilibria in the Nb-Si-Ti alloys with Cr additions via an approach of integrating thermodynamic modeling with designed experiments. The alloying effects of Cr on the microstructure of the Nb-Si-Ti alloys are described using both phase equilibria and solidification paths that were calculated from the thermodynamic description of the Nb-Cr-Si-Ti system developed in the present study.