Functionality of amorphous multicomponent systems largely depends upon the miscibility among components, especially in systems such as amorphous drugs and electrolytes. An in-depth understanding of mixing behaviors of various constituents is necessitated. Here, we applied the small- and wide-angle X-ray scattering (SWAXS) technique to monitor the mixing behaviors in three typical glass-forming binary systems imposed by varied heat of mixing. It is found that the Porod invariant (Q) determined at the glass transition temperature is remarkably enhanced as the concentration fluctuation becomes intensified. Meanwhile, the deviation of Q from the ideal mixing law is markedly weaken at elevated temperatures. The results unambiguously suggest that the degree of concentration fluctuations in mixing systems can be accurately quantified by the structural property, allowing the link to mixing thermodynamics.