The spin-rovibronic energy levels of CaO, which result from the couplings of X(1)Sigma(+), a(3)Pi, A'(1)Pi, b(3)Sigma(+), and A(1)Sigma(+) low-lying electronic states, are determined from wave packet time propagations and Prony analysis. The electronic potentials were taken from our previous study [Chem. Phys., 386, 50 (2011)]. The spin-orbit and (L) over cap coupling functions were determined by CASSCF and MRCI calculations. The effects of spin-orbit coupling on vibrational levels were analyzed in the Omega=0(+), 0(-), 1 coupling schemes. All spin-vibronic energy levels associated with the a(3)Pi, A'(1)Pi, b(3)Sigma(+), and A(1)Sigma(+) states were determined up to 16000 cm(-1) above the electronic ground-state minimum. The results obtained from the spin-orbit coupling functions are in remarkable agreement with the experimental data extracted using a deperturbation procedure. The final energies calculated for J = 2 and J = 25 are used to compare the experimental observations concerning the X(1)Sigma(+)-A(1)Sigma(+) transition. (C) 2011 Elsevier Inc. All rights reserved.