The role of resting frontal alpha-asymmetry in explaining neural-mechanisms of affect and approach/ withdrawal behavior is still debatable. the present study explores the ability of the quasi-stable resting EEG asymmetry information and the associated neurovascular synchronization/desynchronization in bringing more insight into the understanding of neural-mechanisms of affect and approach/withdrawal behavior. For this purpose, a novel frontal alpha-asymmetry based on microstates, that assess quasi-stable EEG scalp topography information, is proposed and compared against standard frontalasymmetry. Both proposed and standard frontal alpha-asymmetries were estimated from thirty-nine healthy volunteers resting-EEG simultaneously acquired with resting-fMRI. Further, neurovascular mechanisms of these asymmetry measures were estimated through EEG-informed fMRI. Subsequently, the Hemodynamic Lateralization index (HLi) of the neural-underpinnings of both asymmetry measures was assessed. Finally, the robust correlation of both asymmetry-measures and their HLI's with PANAS, BIS/BAS was carried out. The standard resting frontal-asymmetry and its HLI yielded no significant correlation with any psychological-measures. However, the microstate resting frontal-asymmetry correlated significantly with negative affect and its neural underpinning's HLI significantly correlated with Positive/Negative affect and BIS/BAS measures. Finally, alpha-BOLD desynchronization was observed in neural-underpinning whose HLI correlated significantly with negative affect and BIS. Hence, the proposed resting microstate-frontal asymmetry better assesses the neural-mechanisms of affect, approach/withdrawal behavior.