Although increasing evidence has reported that unfavorable temperature may lead to increased premature mortality, a systematic assessment is lacking on the impact of ambient temperature on years of life lost (YLL) and life expectancy in China. Daily data on mortality, YLL, meteorological factors and air pollution were obtained from 93 Chinese cities during 2013–2016. A two-stage analytic approach was applied for statistical analysis. At the first stage, a distributed lag non-linear model with a Gaussian link was used to estimate the city-specific association between ambient temperature and YLLs. At the second stage, a meta-analysis was used to obtain the effect estimates at regional and national levels. We further estimated the corresponding YLLs and average life expectancy loss per deceased person attributable to the non-optimum temperature exposures based on the established associations. We observed ‘U’ or ‘J’ shaped associations between daily temperature and YLL. The heat effect appeared on the current day and lasted for only a few days, while the cold effect appeared a few days later and lasted for longer. In general, 6.90% (95% confidence interval (CI): 4.62%, 9.18%) of YLLs could be attributed to non-optimum temperatures at the national level, with differences across different regions, ranging from 5.36% (95% CI: −3.36%, 6.89%) in east region to 9.09% (95% CI: −5.55%, 23.73%) in northwest region. For each deceased person, we estimated that non-optimum temperature could cause a national-averaged 1.02 years (95% CI: 0.68, 1.36) of life loss, with a significantly higher effect due to cold exposure (0.89, 95% CI: 0.59, 1.19) than that of hot exposure (0.13, 95% CI: 0.09, 0.16). This national study provides evidence that both cold and hot weather might result in significant YLL and lower life expectancy. Regional adaptive policies and interventions should be considered to reduce the mortality burden associated with the non-optimum temperature exposures.