This investigation, following our recent report on the one-pot hemi-micellar interfacial synthesis of Janus gold nanoclusters and the inter-cluster electron coupling establishing insulator-metal transition in the oriented Janus monolayers [Langmuir, 2010, 26(17), 14047], was to fabricate modified electrodes for sensing dopamine, the neurotransmitter. With a detection limit in the sub-nanomolar range, the apparent electron transfer rate constants for dopamine detection signified an intricate Janus cluster 2D phase dependency. Surface pressure as a thermodynamic variable controlled the electronic communication between the clusters as a result of varied inter-cluster distance and size, ultimately reflecting on the sensitivity and detection limit for dopamine sensing. The non-covalent nature of the ligands on the core metal clusters facilitated the overall electro-catalytic oxidation of dopamine. The notable feature of this precise work was that it established a more effective phase- and orientation-specific Janus cluster sensing than those reported through patterned gold nanowire based sensors.