A single crystal of alpha-LixV(2)O(5) (x = 0.005) is studied by electron nuclear double resonance spectroscopy (ENDOR). It is shown that the ESR spectrum is composed of two overlapping signals. The first one (A-center) is the well-known 39-line spectrum due to pularons trapped by the Coulomb field of Li+ ions. The second (B-center) is unknown so far and is studied here for the first time. It consists of a broad unresolved line hidden inside the 29-line spectrum. The B-center represents a foe polaron localized on a single vanadium site of one [V2O5](n), layer and is responsible for the compound’s electronic conductivity, The ENDOR lines of this center are assigned to two nearest neighbor vanadium nuclei, one being located in the same [V2O5](n) layer as the polaron while the other belonging to the adjacent layer. ENDOR spectroscopy shows the existence of a significant covalent interaction between layers, in contrast with the usual assumption of Van der Waals interactions. This covalency manifests itself by the transfer of about 10(-2) unpaired polaron spin density into 4s and d(z)2 vanadium orbitals of the closest vanadium ion in the adjacent layer. Bound polarons (A-centers) do not give an ENDOR response. This feature is attributed to an inhomogeneous distribution of Li+ ions in the matrix (in the form of shallow clusters), which provokes a concentration quenching of the ENDOR enhancement.