The metal leaching characteristics and volatile organic compounds (VOCs) of five different types of waste foundry sands were analyzed with the toxicity characteristic leaching procedure (TCLP) and head space-gas chromatography (HS-GC). Microtox and soil dehydrogenase activity (DHA) tests were then used to evaluate the bio-effects of these waste sands. The results showed that due to the different metals poured and casting materials used to make the sand molds, there was significant difference among the five waste foundry sands in the compositions and concentrations of metal and organic pollutants. The concentrations of Fe in the leachates of iron and steel casting waste foundry sand exceeded the maximal allowable concentrations specified in the National Standard of Drinking Water Quality, whereas the As concentration in the leachate of aluminum casting waste foundry sand exceeded the standard. The five waste foundry sands had quite different compositions and levels of VOCs, which resulted in different levels of inhibition effects on the luminescent bacteria (30% and 95%). Additionally, the soil DHA tests suggested that metal pollutants in waste foundry sands may inhibit the soil microbial activity, whereas organics in the sands may slightly promote the microbial activity. The results of this study indicated that the waste foundry sands may pose considerable threat to the environment when improperly disposed.