Most research on micronutrients in maize has focused on maize grown as a monocrop. The aim of this study was to determine the effects of intercropping on the concentrations of micronutrients in maize grain and their acquisition via the shoot. We conducted field experiments to investigate the effects of intercropping with turnip (Brassica campestris L.), faba bean (Vicia faba L.), chickpea (Cicer arietinum L.), and soybean (Glycine max L.) on the iron (Fe), manganese (Mn), copper (Cu) and zinc (Zn) concentrations in the grain and their acquisition via the above-ground shoots of maize (Zea mays L.). Compared with monocropped maize grain, the grain of maize intercropped with legumes showed lower concentrations of Fe, Mn, Cu, and Zn and lower values of their corresponding harvest indexes. The micronutrient concentrations and harvest indexes in grain of maize intercropped with turnip were the same as those in monocropped maize grain. Intercropping stimulated the above-ground maize shoot acquisition of Fe, Mn, Cu and Zn, when averaged over different phosphorus (P) application rates. To our knowledge, this is the first report on the effects of intercropping on micronutrient concentrations in maize grain and on micronutrients acquisition via maize shoots (straw+grain). The maize grain Fe and Cu concentrations, but not Mn and Zn concentrations, were negatively correlated with maize grain yields. The concentrations of Fe, Mn, Cu, and Zn in maize grain were positively correlated with their corresponding harvest indexes. The decreased Fe, Mn, Cu, and Zn concentrations in grain of maize intercropped with legumes were attributed to reduced translocation of Fe, Mn, Cu, and Zn from vegetative tissues to grains. This may also be related to the delayed senescence of maize plants intercropped with legumes. We conclude that turnip/maize intercropping is beneficial to obtain high maize grain yield without decreased concentrations of Fe, Mn, Cu, and Zn in the grain. Further research is required to clarify the mechanisms underlying the changes in micronutrient concentrations in grain of intercropped maize.