A kind of thermoelectric cooling charge-coupled device (CCD) detector is designed and its performance is analyzed. The vacuum refrigeration structure, electric circuit, application software of this CCD detector and their design thoughts, functions and effects are introduced. The dark current noise and the readout noise of this detector are tested. The results show that, the readout noise is 56 e- and the dark current noise is 0.232 e-·(pixel·s)-1 at the temperature of -30 ℃ and the reading frequency of 250 kHz. The spontaneous Raman scattering signal of the ambient atmosphere is obtained by this detector. Under the temperature of -30 ℃ and the exposure time of 10 s, the relative heights of the spontaneous Raman scattering peaks for the O2, N2 and H2O are 3303, 7768, 843 ADU, respectively, in which the signal-background-ratio and the signal-noise-ratio of the N2 peak are 14.8 and 24.9, respectively. The designed CCD detector possesses a detection ability for the weak spontaneous Raman scattering signals.