Nanocrystallline modified BaTiO3 dielectric ceramics (B100 nm) have been developed by different sintering methods. The different TCC characteristics of the nano-BaTiO3-based ceramics caused by different sintering process have been investigated. It is found that the samples fired by the TSS method had a higher dopant concentration in the shell region than those fired by the CS method, which causes the diffuse transition peak shifts to the lower temperature and improves the TCC performance at the cold end.