A suitable carbon source is significant for biological nitrate removal from groundwater. In this study, slow-release carbon sources containing polylactic acid (PLA) and starch at 8:2, 7:3, 6:4, 5:5, 4:6, and 3:7 ratios were prepared using a blending and fusing technique. The PLA/starch blend was then used as a solid carbon source for biological nitrate removal. The carbon release rate of PLA/starch was found to increase with increased starch content in leaching experiments. PLA/starch at 5:5 mass ratio was found to have the highest denitrification performance and organic carbon consumption efficiency in semi-continuous denitrification experiments, and was also revealed to support complete denitrification at 50 mg-N/L influent nitrate concentration in continuous experiments. The effluent nitrate concentration was <2 mg NO3–-N/L, which met the national standard (GB 14848-93) for groundwater. Scanning electron microscopy results further showed that the surface roughness of PLA/starch increased with prolonged experimental time, which may be conducive to microorganism attachment. Therefore, PLA/starch was a suitable carbon source and biofilm carrier for groundwater remediation.