Essential fatty acids (EFA), including linoleic acid (LA) and alpha-linolenic acid (ALA), are indispensable for proper brain growth especially in the first months after birth when it develops most rapidly. Since fats, especially EFA, in breast milk are highly variable between mothers, we indirectly examined whether milk energy, LA and ALA content in breast milk affect volume and shape of the infant's head. The study encompassed 60 mothers and their healthy term-born infants between the third and sixth month of lactation. The percentage of macronutrients and dry matter in human milk samples was assessed using Fourier-transform infrared spectroscopy (FTIR), and LA and ALA concentrations in breast milk were determined using gas chromatography (GC). Infant head measurements were taken using standard anthropometric equipment and methods. LA content in breast milk was found to be positively associated with head volume in boys. Furthermore, ALA content was positively associated with the head height-to-length ratio thus with more arched head in infants irrespective of sex. No relationship was found between milk energy content in mothers' milk and infant head dimensions. This is the first study to demonstrate a relationship between EFA concentration in human milk and infant head dimensions. Given that LA and ALA in human milk are variable in women and due to the extremely rapid growth of nerve tissue in the first months of life, adequate supply of EFA in breast milk should attract the attention of public health sciences.