Taking into account variations in family structure among working mothers, this study examines the effect of family‐support policies on the well‐being of 4,247 female employees in Britain who have never married, are married, or are divorced, separated, or widowed. Based on data from the British Workplace Employment Relations Survey of 2011, the study found that not all family‐friendly policies were equally effective in alleviating anxiety and depression or in fostering job satisfaction among working mothers. Although having the option to work the same number of hours across fewer days per week was shown to be beneficial to the well‐being of never‐married mothers, flextime was beneficial to divorced, separated, or widowed mothers. Having the chance to reduce work hours, work from home, or work only during the school term was most beneficial to the well‐being of married mothers. These findings bolster arguments that the availability of family‐support policies in the workplace enhances the effectiveness of working mothers in both their work and family roles, thereby positively affecting their overall well‐being. They also highlight the role that individuals' family structures may play in the use of those initiatives.