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 66 As. The fusion-evaporation reaction 40 Ca( 28 Si,pn) 66 As was employed at beam energies of 75 and 83 MeV. The half-lives and ordering of two known isomeric states in 66 As 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 66 As, 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 pf 5/2 g 9/2 model space.alignment of the valence nucleons [5], shape changes as a function of spin [6], and the evolution of nuclear radii along the yrast line [7].Two isomeric states have been previously identified in 66 As [8]. In more recent studies, the decay of the isomers was used as a tag to identify excited states above the isomeric states [9] and new prompt γ rays were associated with 66 As, without the ability to observe delayed transitions, in Ref.[10]. In the current work, both the isomeric and the prompt T = 0 and T = 1 structures have been studied. The half-lives and ordering of the isomeric states have been determined with improved accuracy and internal conversion coefficients have been deduced for the transitions deexciting the isomers, allowing the determination of the corresponding experimental B(E2) transition strengths. Recent experimental [10] and theoretical [11] work has investigated the CED in the A = 66 ( 66 As/ 66 Ge) and A = 70 ( 70 Br/ 70 Se) systems. The present work agrees with some of the findings reported in Ref.[10], but differs for the T = 1, I π = 6 + state resulting in a positive CED behavior.The odd-odd N = Z nuclei in the mass A ∼ 60-70 region provide an opportunity to test shell-model (SM) interactions and model spaces for these midmass nuclei. In the present work SM calculations have been performed using the modern JUN45 interaction [12] and a pf 5/2 g 9/2 model space. The experimental results are compared with the SM predictions in terms of level energies, CED, and B(E2) values.