This letter reports the discovery of a remarkably hard spectrum source, HESS J1641-463, by the High Energy Stereoscopic System (H.E.S.S.) in the very-high energy (VHE) domain. HESS J1641-463 remained unnoticed by the usual analysis techniques due to confusion with the bright nearby source HESS J1640-465. It emerged at a significance level of 8.5 standard deviations after restricting the analysis to events with energies above 4 TeV. It shows a moderate flux level of F(E > 1 TeV) = (3.64 +/- 0.44_stat +/- 0.73_sys) x 10^-13 cm^-2s-1, corresponding to 1.8% of the Crab Nebula flux above the same energy, and a hard spectrum with a photon index of Gamma = 2.07 +/- 0.11_stat +/- 0.20_sys. It is a point-like source, although an extension up to Gaussian width of sigma = 3 arcmin cannot be discounted due to uncertainties in the H.E.S.S. PSF. The VHE gamma-ray flux of HESS J1641-463 is found to be constant over the observed period when checking time binnings from year-by-year to the 28 min exposures timescales. HESS J1641-463 is positionally coincident with the radio supernova remnant SNR G338.5+0.1. No X-ray candidate stands out as a clear association, however Chandra and XMM-Newton data reveal some potential weak counterparts. Various VHE gamma-ray production scenarios are discussed. If the emission from HESS J1641-463 is produced by cosmic ray protons colliding with the ambient gas, then their spectrum must extend close to 1 PeV. This object may represent a source population contributing significantly to the galactic cosmic ray flux around the knee.