The mass-resolved excitation spectrum of the B (II1)-I-3-X(1)Sigma(+) transition of HgAr was measured by the two-color resonantly enhanced two-photon ionization method using a high-resolution reflectron time-of-flight mass spectrometer. The rotational structures were recorded with high spectral resolution (similar to 0.05 cm(-1))for the (upsilon(B),0) bands (upsilon(B) = 0 - 9) of a single isotopomer (HgAr)-Hg-200. From the rotational analysis, the presence of an Omega-type doubling was identified for the first time, which is caused by the rotational perturbation from the nearby highly excited vibrational levels of the A (II0+)-I-3 state. The spacing between the Omega-type doublers was found to exhibit a characteristic reversal as a function of upsilon(B). From the deperturbation of the Omega-type doubling, the vibrational level energies of the A state in the vibrationally highly excited region were derived, from which its long-range interaction potential was determined.