Excited state relaxation kinetics of nanostructured poly(di-n-hexyl)silane embedded in nanoporous silica SBA-15 with the pore size of 10 not was considered with the nanosecond and picosecond time resolution by using photomultiplier with fast response time and by means of time correlated two-pulse excitation. Measurements were carried out at room temperature. For comparative reasons the exciton relaxation kinetics of poly(di-n-hexyl,)silane films are also considered. It teas found that the photoluminescence of nanostructured poly(di-n-hexyl)silane decays exponentially with about 6ns time constant, which is more than 10 times longer than that of the film.. The longer decay time should be related with slower exciton diffusion and lower density of exciton quenching centers.