Maize stalks support leaves and reproductive structures and functionally support water and nutrient transport; besides, their anatomical and biochemical characteristics have been described as a plant defense against stress, also impacting economically important applications. In this study, we evaluated agronomical and stem description traits in a subset of maize inbred lines that showed variability for cell wall composition in the internodes. Overall, a great proportion of lignin subunit G and a low concentration of p-coumaric acid and lignin subunit S are beneficial for greater rind puncture resistance and taller plants, with a greater biomass yield. Also, the greater the proportions of subunit H, the longer the internode. Finally, the lower the total hemicellulose content, the greater the rind puncture resistance. Our results confirmed the effect of the cell wall on agronomic and stalk traits, which would be useful in applied breeding programs focused on biomass yield improvement.