Laser-induced tunneling ionization is one of the fundamental light-matter interaction processes. An accurate description of the tunnel-ionized electron wave packet is central to understanding and controlling subsequent electron dynamics. Because of the anisotropic molecular structure, tunneling ionization of molecules involves considerable challenges in accurately describing the tunneling electron wave packet. Up to now, some basic properties of the tunneling electron from molecules still remain unexplored. Here, we demonstrate that the tunneling electron from a molecule is not always emitted from the geometric center of the molecule along the tunnel direction. Rather, the photoemission position depends on the molecular orientation. Using a photoelectron holographic technique, we determine the photoemission position for a nitrogen molecule relative to the molecular geometric center to be $95\pm 21\mathrm{pm}$ when the molecular axis is oriented along the tunnel direction. Our Letter poses, and answers experimentally, a fundamental question as to where the molecular photoionization actually begins, which has significant implications for time-resolved probing of valence electron dynamics in molecules.

• Multiphoton or tunneling ionization & excitation
• Photoemission
• Ultrafast phenomena