The low-lying excited states of Sc46 populated by primary and secondary γ-ray transitions from the Sc45(n, γ)Sc46 thermal-neutron-capture reaction were studied. Ge(Li) detectors were used exclusively in both singles and coincidence γ-ray investigations. High-energy primary γ-ray spectra were obtained and were used to infer the excitation energies of 53 states up to ~2600 keV. The neutron binding energy was determined to be 8767+/-1 keV. Coincidence investigations between high-energy (~7-9 MeV) and low-energy (<~2 MeV) γ rays, as well as among the low-energy transitions, have allowed a total of 23 low-energy transitions to be assigned between states up to an excitation energy of 1324 keV. A level and decay scheme is proposed for a total of 57 excited states below an energy of 2600 keV. This scheme differs in several important respects from those proposed previously. The observed characteristics of these states are compared with the most recent charged-particle reaction studies, previous bent-crystal-spectrometer γ-ray results, and available theoretical calculations.