Photoelectron spectra of (HF)(3)(-) reveal coexistence of two anionic isomers with vertical electron detachment energies (VDE) of 0.24 and 0.43 eV. The results of electronic-structure calculations, performed at the coupled cluster level of theory with single, double, and noniterative triple excitations, suggest that the two isomers observed experimentally are an open, zigzag, dipole-bound anion and an asymmetric solvated electron, in which the dipole-bound anion of (HF)(2) is solvated by one HF monomer at the side of the excess electron. The theoretical VDE of 0.21 and 0.44 eV, respectively, are in excellent agreement with the experimental data.