Proximity effect, which refers to the low-lying (n,π*) and (π,π*) states with close energy levels, usually plays a negative role in the luminescent behaviors of heterocyclic luminogens. However, no systematic study attempts to reveal and manipulate proximity effect on luminescent properties. Here, we report a series of methylquinoxaline derivatives with different electron-donating groups, which show different photophysical properties and aggregation-induced emission behaviors. Experimental results and theoretical calculation reveal the gradually changed energy levels and different coupling effects of the closely related (n,π*) and (π,π*) states, which intrinsically regulate proximity effect and aggregation-induced emission behaviors of these luminogens. With the intrinsic nature of heterocycle-containing compounds, they are utilized for sensors and information encryption with dynamic responses to acid/base stimuli. This work reveals both positive and negative impacts of proximity effect in heterocyclic aggregation-induced emission systems and provides a perspective to develop functional and responsive luminogens with aggregation-induced emission properties.