Single-particle and collective excitations in 66 Zn have been investigated via the multinucleon transfer reaction, 26 Mg( 48 Ca, α4nγ ) using the Gammasphere multidetector array and the Fragment Mass Analyzer. In addition to confirming and complementing the previously known low-spin structure, a new quasirotational band comprising several stretched E 2 transitions has been established to high spins. However, due to fragmentary nature of its decay, it was not possible to link this sequence to the low-lying states and, thus, determine the absolute excitation energies, spins, and parities unambiguously. Large-scale shell-model calculations employing the JUN45 and jj44b effective interactions are able to successfully describe the low-spin structure and herewith confirm that it is dominated by single-particle excitations. The newly established rotational cascade is compared with known superdeformed bands in the A ≈ 60-70 mass region, and with results of calculations performed within the frameworks of the cranked shell model and the adiabatic and configuration-fixed constrained covariant density functional theory and the quantum particle-rotor model.