The solidification of a multicomponent stainless steel slag and dust composite has been studied by thermodynamic calculations using Factsage and analyses of samples using EPMA and Rietveld refinement of synchrotron X-ray powder diffraction after various cooling rates. At an apparent cooling rate of 1 K/min, the content of spinel (10.6 wt%) was less than thermodynamically calculated (16.6 wt %), largely because of difficulties in the diffusion of depleted ions (including Cr, Mn, and Ni) in the liquid with very gradual compositional gradients. Melilite showed a uniform but distorted crystal structure of P21212 and its content (48.9 wt%) was larger than the calculated result (32.3 wt%). At apparent cooling rates of 10 K/min and 50 K/min, a slight decrease in spinel and a significant decrease in melilite were observed, and the spinel was divided into two regions with an identical space group of Fd3m but with distinguished composition and lattice parameters. However, the amorphous proportion consistently increased with the cooling rate from 29.4 wt% at 1 K/min to 69.6 and 92.9 wt% at 10 K/min and 50 K/min respectively.