Exposures to ambient fine particulate matter (PM(2.5)) and cold ambient temperatures have been identified as important risk factors in contributing towards the global mortality from chronic obstructive pulmonary disease (COPD). Despite China currently being the country with the largest population in the world, previous relative risk (RR) models have considered little or no information from the ambient air pollution related cohort studies in the country. This likely provides a less accurate picture of the trend in air pollution attributable mortality in the country over time. A novel relative risk model called pollutant-temperature exposure (PTE) model is proposed to estimate the RR attributable to the combined effect of air pollution and ambient temperature in a population. In this paper, the pollutant concentration-response curve was extrapolated from the cohort studies in China, whereas the temperature response curve was extracted from a study in Yangtze River Delta (YRD) region. The performance of the PTE model was compared with the integrated exposure-response (IER) model using the data of YRD region, which revealed that the estimated relative risks of the PTE model were noticeably higher than the IER model during the winter season. Furthermore, the predictive ability of the PTE model was validated using actual data of Ningbo city, which showed that the estimated RR using the PTE model with 1-month moving average data showed a good result with the trend of actual COPD mortality, indicated by a lower root mean square error (RMSE = 0.956). By considering the combined effect of ambient air pollutant and ambient temperature, the PTE model is expected to provide more accurate relative risk estimates for the regions with high levels of ambient PM(2.5) and seasonal variation of ambient temperature.