Positive deviance inquiry is effective in identifying advantageous health behaviors and improving health outcomes among disadvantaged resource-poor populations. The objective of this study was to apply the positive deviance concept to explore the characteristics of positive deviants for breastfeeding among WIC-enrolled first-time mothers in Louisiana. The cross sectional study included data on 2,036 WIC-enrolled first time mothers (52.6% black) from the LaPRAMs, 2000-2004. Chi-square test was used to compare groups. Multivariable logistic regression was applied to calculate adjusted OR and 95% CI by breastfeeding initiation status. The average age was 21.3 years, 31.5% had less than 12 years of education, and 44.6% of the sample reported having initiated breastfeeding. Black mothers were less likely to initiate breastfeeding than their white counterparts (OR 0.39 (95% CI: 0.31, 0.48)). Among 641 WIC-enrolled first time mothers with less than 12 years of education, 28.4% were identified as positive deviants for breastfeeding initiation. Among the black mothers 19.8% were positive deviants compared to 40.3% of the white mothers. Breastfeeding in the hospital after delivery (P < 0.0001) and having received help on how to breastfeed in the hospital (P < 0.0001) were significantly associated with breastfeeding initiation in white and black mothers. In addition, the black positive deviants were more likely, OR 2.80 (95% CI: 1.20, 6.56) to have initiated breastfeeding if their baby was low birth weight. Breastfeeding practices shortly after delivery including assistance and education from staff in the hospital, are related to breastfeeding initiation among less educated WIC-enrolled mothers.