We report the high-resolution photoassociation (PA) spectroscopy of ²³Na excited from the spin-1 Bose-Einstein Condensate (BEC) to the molecular state of 0g−(P _3/2)v = 4 and 1 _g(P _3/2)v = 91. By comparing the PA spectra of different spin configurations, we experimentally studied the effect of spin on the PA spectra. The experimental spectra comply well with the theoretical consideration. The results will play an important role in the study of the spin interaction and control of the antiferromagnetism in Na.