Light-emitting diodes (LEDs) have recently been widely used as light sources for the cultivation of plants in controlled environments. However, before LEDs can be used as the sole light source, it is imperative that soybean (Glycine max) response to light quality be well characterized. The objective of the present work was to investigate how soybean seedlings respond to different blue (B) and red (R) photon flux ratios (PFR) using LEDs. Light treatments were comprised of 170 ± 5 μmol m−2 s−1 photosynthetic photon flux density with B:R ratios of 0B:100R%, 10B:90R%, 25B:75R%, 50B:50R%, 80B:20R%, 90B:10R%, and 100B:0R%. Our results suggest that with the increase in B PFR from 0 to 90%, both plant height and specific leaf area inclined to decline while stem diameter gradually increased. The plants exposed to 80B:20R% showed unexpectedly greater total root length, root surface area, root volume, number of root tip, plant dry mass, leaf dry mass, root dry mass, leaf mass fraction and root mass fraction than plants exposed to all other treatments. Plants grown with 0B:100R% had the highest content of chlorophyll b (Chl b) and content of total chlorophyll [Chl (a + b)] but possessed the lowest ratio of the content of chlorophyll a to the content of chlorophyll b (Chl a/b). Plants grown with R alone also showed the lowest chlorophyll fluorescent parameters. The light-saturated CO2 assimilation rate (Asat) and the light-saturated stomatal conductance (gssat) for 0B:100R% were, respectively, 64.85% and 203.23% lower than those for 80B:20R%. However, plants grown with sole R accumulated higher soluble sugar and starch content during the daytime. Collectively, our results suggest that compared to R- or B-LED alone, an appropriate combination of R and B promotes plant growth and photosynthetic performance for soybean.