A novel charring agent tris(2‐hydrooxyethyl) isocyanurate terephthalic acid ester, tetramer (TT4) was synthesized using tris(2‐hydrooxyethyl) isocyanurate and terephthalic acid as raw materials, and it was characterized by Fourier transformed infrared spectrometry and 1H‐NMR spectrum. It was combined with ammonium polyphosphate (APP) to form intumescent flame retardants for polylactide (PLA). The combustion properties and thermal stability of PLA/APP/TT4 composites were evaluated by UL‐94 burning tests, limiting oxygen index (LOI), and thermogravimetric analyses (TGA). It was found PLA with 30 wt % of APP/TT4 (5 : 1) achieved UL‐94 V‐0 rating and a 40.6 LOI value. Results from TGA demonstrated that APP/TT4 composites could retard the degradation of PLA above 410°C. The char residue at 500°C is higher than 24%, showing a good char forming ability. Moreover, the continuous and expansionary char layer observed from the SEM images proved good charring forming ability of TT4. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41218.