The single-nucleon knockout reactions 9Be(14B, 13B + gamma)X and 197Au(14B, 13B + gamma)X, at an incident energy of 60 MeV per nucleon, have been used to probe the structure of 14B and of the core fragment 13B. A dominant 2s configuration is deduced for the neutron in the ground state of 14B. The longitudinal momentum distribution for this state is consistent with "neutron halo" structure. Spin assignments for 13B excited states at 3.48 and 3.68 MeV are proposed based on the observed spectroscopic factors for one-neutron removal.