Using data from 60th round of the National Sample Survey, this study attempts to measure the incidence and intensity of ‘catastrophic’ maternal health care expenditure and examines its socio-economic correlates in urban and rural areas separately. Additionally, it measures the effect of maternal health care expenditure on poverty incidence and examines the factors associated with such impoverishment due to maternal health care payments. We found that maternal health care expenditure in urban households was almost twice that of rural households. A little more than one third households suffered catastrophic payments in both urban and rural areas. Rural women from scheduled tribes (ST) had more catastrophic head counts than ST women from urban areas. On the other hand, the catastrophic head count was greater among illiterate women living in urban areas compared to those living in rural areas. After adjusting for out-of-pocket maternal health care expenditure, the poverty in urban and rural areas increased by almost equal percentage points (20% in urban areas versus 19% in rural areas). Increasing education level, higher consumption expenditure quintile and higher caste of women was associated with increasing odds of impoverishment due to maternal health care expenditure. To reduce maternal health care expenditure induced poverty, the demand-side maternal health care financing programs and policies in future should take into consideration all the costs incurred during prenatal, delivery and postnatal periods and focus not only on those women who suffered catastrophic expenditure and plunged into poverty but also those who forgo maternal health care due to their inability to pay.