Here, we report the role of crystal structure and crystal size on the photoluminescence properties of Ce3+ ions in Y2SiO5 nanocrystals. The emission at 430 nm (5d(1) --> 4f(1)) and lifetime of the excited state of Ce3+ ion doped Y2SiO5 nanocrystals are found to be sensitive to the crystal structure, crystal size, and dopant concentration. It is found that the overall lifetime of 0.5 mol % Ce doped Y2SiO5 nanocrystals are 8.78 and 3.45 ns for 1000 and 1100 degreesC heat-treated samples with the same crystal structure (X-1-Y2SiO5 phase), respectively. However, a significant increase in the overall lifetime (35.21 ns) is observed for the 1300 degreesC annealed 0.5 mol % Ce doped Y2SiO5 sample having a different crystal structure (X-2-Y2SiO5 phase). We found that the decay kinetic is biexponential. It is explained that the fast component arises due to sequential hole-electron capture on the luminescent ions and the slow component arises from isolated ions. Our analysis suggests that modifications of radiative and nonraditive relaxation mechanisms are due to local symmetry structure of the host lattice and crystal size, respectively.