In this work, the fundamental mechanism of ultrabright fluorescence from surface-modified colloidal silicon quantum dots is investigated in depth using ultrafast spectroscopy. The underlying energy band structure corresponding to such highly efficient direct bandgap-like emissions in our surface-modified silicon quantum dots is unraveled by analyzing the transient optical spectrum, which demonstrates the significant effect of surface molecular engineering. It is observed that special surface modification, which creates novel surface states, is responsible for the different emission wavelengths and the significant improvement in the photoluminescence quantum yields. Following this essential understanding, surface-modified silicon quantum dots with deep blue to orange emission are successfully prepared without changing their sizes.