[en] A new spectroscopic method that utilizes microwave transition of ultracold molecules is demonstrated. The narrow spectral linewidth (approximately 100 Hz) was guaranteed by preparing molecules at low temperature, and a high signal-to-noise ratio was achieved by preparing a significant fraction of molecules in the target internal state. The repetition rate of the experiment was approximately 10 Hz, which was only limited by the time needed to load ultracold atoms into the magneto-optical trap. To demonstrate the performance, we investigated the hyperfine structures of the vibrational ground states of the $X^1{\mathrm{\Sigma <!--\; ??\; -->}}^{+}$ and $b^3{\mathrm{\Pi <!--\; ??\; -->}}_{0^{+}}$ states of KRb molecules. This technique not only allows us to pursue the narrow-line laser cooling of KRb molecules, but also provided us with essential information for realizing precision spectroscopies e.g., the search for the temporal variation of the electron-to-proton mass ratio. (paper)