The silica‐PI hybrid self‐standing films with ordered mesoporous structure have been prepared by using dibenzoyl‐L‐tartaric acid (L‐DBTA) as non‐surfactant template under mild sol–gel route. Polyimide matrix was obtained from polyamic acid (PAA) via thermal imidization process and the template was removed in this process. The PI‐based hybrid film with 20 wt% SiO2 obtained from DBTA presented the ordered mesoporous channels with average pore size of about 2.0 nm and BET surface area of 1167 m2/g. FTIR and SEM studies indicated that the hydrogen bond interaction between the carboxylic groups of DBTA and benzamide bonds of PAA made the PAA possibly participate in the assembly process of the aggregates of the non‐surfactant template molecules. The mechanical, thermal and some physical properties of these hybrid films materials were also characterized. Copyright © 2010 John Wiley & Sons, Ltd.