Complex spectra of the KRb 420 nm system are analyzed by mass-resolved resonance enhanced two-photon ionization in a cold molecular beam. Vibronic structures of three singlet-singlet (4(1)Π, 7(1)Σ(+), and 5(1)Π←X(1)Σ(+)) transitions were identified for the first time. By comparing with highly accurate ab initio calculations, we assigned the singlet excited electronic states, and determined their electronic term values and vibrational constants. Weak singlet-triplet transitions were observed and identified as the 5(3)Π(0(+))←X(1)Σ(+) transitions by the homogeneous perturbation selection rule.