This paper reports on the development of a technology involving 100Mo-enriched scintillating bolometers, compatible with the goals of CUPID, a proposed next-generation bolometric experiment to search for neutrinoless double-beta decay. Large mass (∼1 kg), high optical quality, radiopure 100Mo-containing zinc and lithium molybdate crystals have been produced and used to develop high performance single detector modules based on 0.2–0.4 kg scintillating bolometers. In particular, the energy resolution of the lithium molybdate detectors near the Q-value of the double-beta transition of 100Mo (3034 keV) is 4–6 keV FWHM. The rejection of the α-induced dominant background above 2.6 MeV is better than 8σ. Less than 10 μBq/kg activity of 232Th(228Th) and 226Ra in the crystals is ensured by boule recrystallization. The potential of 100Mo-enriched scintillating bolometers to perform high sensitivity double-beta decay searches has been demonstrated with only 10 kg×d exposure: the two neutrino double-beta decay half-life of 100Mo has been measured with the up-to-date highest accuracy as T1/2 = [6.90 ± 0.15(stat.) ± 0.37(syst.)] × 1018 years. Both crystallization and detector technologies favor lithium molybdate, which has been selected for the ongoing construction of the CUPID-0/Mo demonstrator, containing several kg of 100Mo.