Experimental results show an intriguing phenomenon that although Bi and Sb have the same number of valence electrons, Bi/Sb substitution increases the electron concentration of n-type Mg3Sb2-based materials. Using a combination of theoretical calculations and experimental synthesis, this work reveals the physical mechanism of the effect of Bi doping on carrier concentration. The increase in electron concentration mainly originates from the enhanced degree of ionization of donor impurity because of the decrease of conductivity effective mass and increase of dielectric constant caused by the narrowing of bandgap with Bi doping. Based on the collaborative optimization of the electrical and thermal transports, n-type Mg3.175Mn0.025Sb1.48Bi0.48Te0.04 exhibits the best thermoelectric performance with a peak zT of 1.85 at 725 K and an average zT of 1.21. This work demonstrates an effective strategy of bandgap engineering for the optimization of carrier concentration and provides insightful guidance for designing other thermoelectric materials.