Porous oil-containing polyimide (PI)/hollow mesoporous silica nanospheres (HMSNs) composite films of PI/HMSNs were fabricated by infusing liquid paraffin into the pores under vacuum. The microstructure, oil storage capability and tribological behaviors of porous oil-containing PI/HMSNs composite films were evaluated using the porous oil-containing PI film as comparisons. As a result, the addition of HMSNs could greatly improve the oil content and oil retention, realizing the intended goals that the prepared oil-containing composites could effectively reduce the friction coefficient and extend the wear life. Besides, liquid paraffin in the porous PI/HMSNs composite films released stably under the actions of the applied load and the friction heat, which can be used in high temperature and load conditions.