The objective was to describe maternal and neonatal characteristics and early neonatal mortality rate according to place of delivery in Greater Metropolitan São Paulo, Brazil. The study linked the databases on live births and early neonatal deaths with the national hospital registry. Place of delivery was identified through certificates of live birth. There were a total of 154,676 live births: 98.7% in-hospital; 0.3% home deliveries, and 1% in other health services. Deliveries in birthing centers and small hospital units were associated with low obstetric risk and a low proportion of preterm and low birth weight infants, and as a result these services showed the lowest early neonatal mortality rate. Compared to hospital maternity ward deliveries, the early neonatal mortality rate was 4.7 times higher for home deliveries and 9.6 higher for emergency room deliveries. There is a high rate of hospital delivery care in São Paulo, but there is still a small portion of accidental home births and deliveries occurring in inappropriate health services, probably as a result of obstetric emergencies and difficulties in accessing hospital services.