The main aim of this study is to identify and investigate specific humates (Hs) as potential biostimulants. Five specialty lignosulfonates (LS1-5), one commercial leonardite-humate (PH), and one commercial lignosulfonate (LH), were analyzed for their carbon, nitrogen, and sulfur contents, and the distribution of functional groups using Fourier transform infrared (FTIR) and Raman spectroscopies. Hs were further supplied for two days to Zea mays L. in hydroponics to test their capacity to trigger changes in physiological target-responses. LS1, LS2, LS3, and LS5 determined the most pronounced effects on plant growth and accumulation of proteins and phenolics, perhaps because of their chemical and spectroscopic features. Root growth was more increased (+51–140%) than leaf growth (+5–35%). This effect was ascribed to higher stimulation of N metabolism in roots according to the increased activity of N-assimilation enzymes (GS and GOGAT) and high consumption of sugars for energy-dependent processes. Increased values of RuBisCO, SPAD (Soil Plant Analysis Development values), and leaf sugar accumulation refer to enhanced photosynthesis attributed to Hs. We conclude that Hs tested in this study functioned as biostimulants, but the specialty lignosulfonates were more efficient in this role, possibly because of the type of starting material and process used for their production, which may have influenced their chemical properties.