Vanadium monoxide cation VO+(X-3 Sigma(-)) has been investigated by two-color -visible (VIS)-ultraviolet (UV) pulsed field ionization-photoelectron (PFI-PE) methods. The unambiguous rotational assignment of rotationally selected and resolved VIS-UV-PFI-PE spectra thus obtained confirms the ground state term symmetry of VO+ to be X-3 Sigma(-). The rotational analysis also yields the rotational constants B-e(+) = 0.5716 +/- 0.0012 cm(-1) and alpha(+)(e) = 0.0027 0.0005 cm(-1) for VO+(X3E-), from which the equilibrium bond distance of VO+(X-3 Sigma(-)) is determined to be alpha(+)(e) = 1.557 +/- 0.002 A. This PFI PE study covers the vibrational bands, VO+(X3E-; v = 0, 1, 2, and 3) <- VO(X-4 Sigma(-); v '' = 0), which has made possible the determination of the vibrational constants for VO+(X(3)Z(-)) to be We = 1068.0 +/- 0.7 cm(-1) and omega(+)(e)x(e)(+) = 5.5 +/- 0.7 cm(-1). The present state-to-state measurement also yields a more precise value (58 380.0 0.7 +/- 0.7 cm(-1) or 7.23820 +/- 0.00009 eV) for the ionization energy of VO [IE(VO)]. This value along with the known IE(V) has allowed the determination of the difference between the 0 K bond dissociation energy (D-0) of VO+(X-3 Sigma(-)) and that of VO(X-4 Sigma(-)) to be D-0(V+-O) - D-0(V-O) = IE(V) - IE(VO) = =3967 +/- 1 cm(-1).