An in-beam study has been performed to further investigate the known isomeric decays and to identify T = 1 excited states in the medium-heavy N = Z = 33 nucleus 66As. The fusion-evaporation reaction 40Ca(28Si,pn) 66As was employed at beam energies of 75 and 83 MeV. The half-lives and ordering of two known isomeric states in 66As have been determined with improved accuracy. In addition, several prompt γ -ray transitions from excited states, both bypassing and decaying to the isomeric states in 66As, have been observed. Most importantly, candidates for the 4+ → 2+ and 6+ → 4+ transitions in the T = 1 band have been identified. The results are compared with shell-model calculations using the modern JUN45 interaction in the pf5/2g9/2 model space.