Ambient cold is associated with substantial population attributable fraction of mortality in China, and respiratory health is vulnerable to cold exposure. This study aimed to examine the effect of cold spells on risk of deaths from chronic obstructive pulmonary disease (COPD). We collected daily data on deaths from COPD and climatic factors from 1 January 2016 to 31 December 2019 in 13 cities of Jiangsu Province, China. We used a quasi-Poisson generalized linear model coupled with a distributed lag non-linear model to quantify the association between risk of COPD deaths and exposure to cold spells (defined as 2 or more consecutive days with mean temperature ≤ 5(th) percentile of daily mean temperature distribution in cold months). Stratification analyses by age, sex, education, and occupation were undertaken to identify vulnerable subgroups. The results suggested that exposure to cold spells was associated with a higher risk of COPD deaths in Lianyungang (relative risk (RR): 1.70; 95% confidence interval (CI): 1.31, 2.21), Nanjing (RR: 1.54; 95% CI: 1.16, 2.04), Nantong (RR: 1.97; 95% CI: 1.68, 2.31), Suzhou (RR: 1.97; 95% CI: 1.55, 2.50), Suqian (RR: 1.68; 95% CI: 1.23, 2.29), Taizhou (RR: 1.70; 95% CI: 1.32, 2.19), Wuxi (RR: 1.99; 95% CI: 1.53, 2.60), Xuzhou (RR: 1.71; 95% CI: 1.01, 2.90), Yancheng (RR: 1.78; 95% CI: 1.53, 2.06), Yangzhou (RR: 2.78; 95% CI: 2.06, 3.76), and Zhenjiang (RR: 1.79; 95% CI: 1.26, 2.55). All subgroups seemed to be vulnerable to the effect of cold spells. The recommendation of this study is that individuals with pre-existing COPD, regardless of age, sex, education, or occupation, should be made aware of the health risk posed by cold spells and should be encouraged to take cold adaptation actions before cold season arrives. The main limitation of this study is that it is subject to ecological fallacy.