Electronic conductance through a single molecule is sensitive towards its structural orientation between two electrodes, owing to the distribution of molecular orbitals and their coupling to the electrode levels, that are governed by quantum confinement effects. Here, we vary the contact geometry of the porphine molecule by attaching two Au tip electrodes that resemble the mechanical break junction, via thiol anchoring groups. We investigate the current‐voltage characteristics of all the contact geometries using non‐equilibrium Green’s function formalism along with density functional theory and tight‐binding framework. We observe varying current responses with changing contact sites, originating from varied wave‐function delocalization and quantum interference effect. Our calculations show asymmetric current‐voltage characteristics under forward and reverse biases due to structural asymmetry of the tip electrodes in either sides of the molecule. We establish this phenomenon as a universal feature for any molecular electronic device, irrespective of the inherent structural symmetry of a molecule. This will provide fundamental insights of electronic transport through single molecule in real experimental setup. Furthermore, our observations of varying current response can further motivate the fabrication of sensor devices with porphine based biomolecules that control important physiological activities, in view of their applications in advanced diagnostics.This article is protected by copyright. All rights reserved.