High-resolution optical spectrometers are crucial in revealing intricate characteristics of signals, determining laser frequencies, measuring physical constants, identifying substances, and advancing biosensing applications. Conventional spectrometers, however, often grapple with inherent trade-offs among spectral resolution, wavelength range, and accuracy. Furthermore, even at high resolution, resolving overlapping spectral lines during spectroscopic analyses remains a huge challenge. Here, we propose a vector spectrometer with ultrahigh resolution, combining broadband optical frequency hopping, ultrafine microwave-photonic scanning, and vector detection. A programmable frequency-hopping laser was developed, facilitating a sub-Hz linewidth and Hz-level frequency stability, an improvement of four and six orders of magnitude, respectively, compared to those of state-of-the-art tunable lasers. We also designed an asymmetric optical transmitter and receiver to eliminate measurement errors arising from modulation nonlinearity and multi-channel crosstalk. The resultant vector spectrometer exhibits an unprecedented frequency resolution of 2 Hz, surpassing the state-of-the-art by four orders of magnitude, over a 33-nm range. Through high-resolution vector analysis, we observed that group delay information enhances the separation capability of overlapping spectral lines by over 47%, significantly streamlining the real-time identification of diverse substances. Our technique fills the gap in optical spectrometers with resolutions below 10 kHz and enables vector measurement to embrace revolution in functionality.