Based on different neutron star–white dwarf (NS-WD) population models, we investigate the prospects of gravitational-wave (GW) detections for NS-WD mergers, with the help of early warnings from two space-borne decihertz GW observatories, DO-Optimal and DECIGO. We not only give quick assessments of the GW detection rates for NS-WD mergers with the two decihertz GW detectors, but also report systematic analyses on the characteristics of GW-detectable merger events using the method of Fisher matrix. With a sufficient one-day early-warning time, the yearly GW detection number for DO-Optimal is in the range of (1.5–1.9) × 103, while it is (3.3–4.6) × 104 for DECIGO. More importantly, our results show that most NS-WD mergers can be localized with an uncertainty of $\mathcal {O}(10^{-2})\, \mathrm{deg}^2$. Given the NS-WD merger as a possible origin for a peculiar long-duration gamma-ray burst, GRB 211211A, followed with kilonova-like emissions, we further suggest that the GW early-warning detection would allow future electromagnetic telescopes to get prepared to follow-up transients after some special NS-WD mergers. Based on our analyses, we emphasize that such a feasible ‘wait-for’ pattern can help to firmly identify the origin of GRB 211211A-like events in the future and bring excellent opportunities for the multimessenger astronomy.