Toluenediamine (TDA) tar, as the heavy fraction from the dinitrotoluene hydrogenation to produce the important product of TDA, contains significant amounts of meta-TDA of 10 - 30 wt.% and is currently incinerated as waste at great cost. In this paper, the adsorption separation technology was adopt for the recovery of meta-TDA from TDA tar with some porous adsorbent materials. The activated carbon has the highest adsorption ratio for ethanol solution of meta-TDA. After treatment by HNO3 or CH3COOH, the modified activated carbon has the slightly decreased adsorption capacity for TDA tar of 238.8 mg·g-1 or 243.3 mg·g-1 with the meta-TDA selectivity of 96.36 % or 98.15 %. While the activated carbon modified by NaOH or NH3·H2O leads to the higher adsorption capacity of 287.9 mg·g-1 or 261.2 mg·g-1 for TDA tar with relative lower meta-TDA selectivity of 90.10 % or 96.02 %. The FT-IR and BET results confirm that surface oxygen-containing groups can be created through the acid or alkali modification, which result in enhancing the adsorption selectivity of meta-TDA. The proposed selective adsorption based on modified activated carbon would be an efficient and low-cost separation technology for TDA recovery from TDA tar.