Accurate spectroscopic constants and rovibrational level information are of great importance in molecular physics and astrophysical field. In this work, a new computational scheme is presented to further improve the accuracy of spectroscopic constants, and the two lowest electronic states of sulfur monoxide molecule are investigated as a typical case study. High-level ab initio calculations are carried out to compute the potential energy curves (PECs) of the lowest bound states, the ground triplet states X3Σg-, and the first excited singlet states a1Δg of SO molecule. The explicitly correlated multi-reference configuration interaction method (MRCI-F12) and cc-pCVQZ-F12 basis set are adopted in the electronic structure computations. The Davidson correction is taken into account to eliminate the size-consistency error. The core-valence (CV) electron correlations of the n=2 shell of S atom and n=1 shell of O atom are estimated by the MRCI-F12 method, whereas only the 1 s orbital of S atom is excluded in the CV calculations. Moreover, we introduce the scalar relativistic effect into our study by utilizing the second-order Douglas-Kroll and Hess (DKH) one-electron integrals by the MRCI method through combining with the uncontracted cc-pCVQZ-F12 basis set. On the basis of the PECs of the SO dimer, the spectroscopic constants (Te, Re, ωe, ωeχe, Be, αe and De) of the two electronic states are determined by solving the one-dimensional nuclear rovibrational Schrödinger equations. Our spectroscopic constants are found to be in excellent agreement with previous experimental and theoretical values. Furthermore, the detailed information about the vibrational energy levels and rotation spectroscopic constants (Bν, Dν) of the two states is also presented with a deviation of 0.1% order of magnitude from the available experimental results. Our present computational work is valuable for future experimental studies on the rovibrational energy levels for the SO molecule and also indicates that the MRCI-F12 approach is cheap and accurate and expected to have wide applications in the PECs of other small molecular systems.