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We report magnetic dipole field investigation at the atomic scale in a single crystal of quasi-one-dimensional (Q1D) paramagnetic conductor Li0.9Mo6O17, using a paramagnetic electron model and (7)Li-NMR spectroscopy measurements with an externally applied magnetic field B 0  =  9 T. We find that the magnetic dipole field component ([Formula: see text]) parallel to B 0 at the Li site from the Mo electrons has no lattice axial symmetry; it is small around the middle between the lattice a and c axes in the ac-plane with the minimum at the field orientation angle [Formula: see text], while the [Formula: see text] maximum is at [Formula: see text] when B 0 is applied perpendicular to b ([Formula: see text]), where [Formula: see text] represents the direction of [Formula: see text]. Further estimation indicates that [Formula: see text] has a maximum value of 0.35 G at B 0  =  9 T. By minimizing the potential magnetic contributions to the NMR spectra satellites with the NMR spectroscopy measurements at the direction where the value of the magnetic dipole field component [Formula: see text] is  ∼0, the behavior of the electron charge statics is exhibited. This work demonstrates that the magnetic dipole field of the Mo electrons is the dominant source of the local magnetic fields at the Li site, and suggests that the unknown metal-'insulator' crossover at low temperatures is not a charge effect. The work also reveals valuable local electric and magnetic field information for further NMR investigation as recently suggested (2012 Phys. Rev. B 85 235128) regarding the unusual properties of the material.