Associations between GABAergic and glutamatergic systems and measures of brain connectivity have been reported previously. However, there is currently no evidence for associations between these systems and local connectivity measures, limiting our understanding of inhibitory/excitatory balance and connectivity across differing spatial ranges. We demonstrated that only regional connectivity and spontaneous activity, but not long-range connectivity, were associated with GABA and GABA/Glx ratio in the ACC. We suggest that this correlation between measures of intra-regional connectivity and GABA in the ACC may be driven by interneuron activity. Further, associations between neurotransmitter pools and inter-regional connectivity may be region/network and context-specific.