The development of green and simple chemiluminescence (CL) systems with intensive and long-lasting emission is highly desirable in lighting and extension of their applications. In this study, it is found that the involvement of aggregation-induced emission (AIE) surfactant could greatly enhance the CL of luminol–H2O2–Co2+ system. The inserted hydrophobic tetraphenylethylene fluorophore in AIE is able to increase the hydrophobicity of alkyl chain and decrease the critical micelle concentration (CMC) of surfactant. The synergistic effect of micelle-improved enrichment and CL resonance energy transfer endows luminol–H2O2–Co2+ system intensive and long-lasting emission under neutral pH conditions (pH 7.4). The visible emission is still observed even after 60 min. Our study has opened a new avenue for exploring green and simple effective CL systems through AIE surfactant with unltralow CMC toward various applications in lighting, optical sensing, and photocatalysis, etc.