This research assessed the underlying psychometric multidimensionality and nomological validity of 523 employees' responses to the Work-related Basic Need Satisfaction (W-BNS) scale using bifactor-exploratory structural equation modeling (bifactor-ESEM). Our results first showed the superiority of a bifactor-ESEM representation when compared to alternative representations of the data. Thus, employees' ratings of psychological need satisfaction simultaneously reflected a global need satisfaction construct, which coexisted with specific autonomy, competence, and relatedness needs satisfaction. Importantly, our findings also supported the nomological validity of employees' ratings of psychological need satisfaction in relation to measures of positive affect, negative affect, job satisfaction, perceived organizational support, organizational citizenship behaviors, work engagement, and burnout. In addition, our results also supported the presence of indirect (mediated) effects between perceived organizational support and some of the outcome variables as mediated by employees' levels of need satisfaction.