Excited states in the N=102 isotones 166Gd and 164Sm have been observed following isomeric decay for the first time at RIBF, RIKEN. The half-lives of the isomeric states have been measured to be 950(60) and 600(140) ns for 166Gd and 164Sm, respectively. Based on the decay patterns and potential energy surface calculations, including β6 deformation, a spin and parity of 6- has been assigned to the isomeric states in both nuclei. Collective observables are discussed in light of the systematics of the region, giving insight into nuclear shape evolution. The decrease in the ground-band energies of 166Gd and 164Sm (N=102) compared to 164Gd and 162Sm (N=100), respectively, presents evidence for the predicted deformed shell closure at N=100.