Promoting industrial ecology and greening is the fundamental requirement of the new development concept, and also the key to realizing high-quality and sustainable development of regional economy. This paper selects the relevant data of eight cities in Anhui section of Huaihe River Economic Belt from 2014 to 2018, and uses the entropy method and the undesirable SBM model to calculate the industrial development level and ecological efficiency during the study period. Moreover, based on the coupling coordination degree model, the synergistic effect between industrial development and ecological efficiency is analyzed, and the spatial-temporal evolution pattern between them is clarified by means of spatial econometric analysis model. Further research suggests that: (1) the synergistic effect between industrial development and ecological efficiency in Anhui section of Huaihe River Economic Belt from 2014 to 2018 is significant, showing a steady strengthening trend. The endogenous power of industrial development keeps strengthening, and the scale effect keeps spillover diffusion. The mean value of overall coupling coordination degree is generally between 0.6 and 0.7. (2) In terms of spatial distribution, the regions with high coupling coordination degree are mainly distributed in the eastern part of Anhui Section (Bengbu and Chuzhou), the lower level area is mainly distributed in the northern part of Anhui Section (Suzhou), and the middle level area is widely distributed. (3) The agglomeration of coupling coordination degree between industrial development and ecological efficiency mainly occurs in low-high (L-H) and high-low (H-L) agglomeration areas. (4) The level of economic development, intensity of R&D and intensity of environmental regulation have significant positive effects on the coupling coordination degree of industrial ecological efficiency and industrial development, and promote the increase of coupling coordination effect. Finally, based on the research results, targeted suggestions are put forward in order to promote the coupling coordination between industrial development and ecological civilization construction, and walk out of a new road of high-quality development of green ecology.