It is vital for China to investigate the coupling and coordination relationship between technological innovation and ecological environment to accomplish its high-quality development strategy currently. In order to solve the question mentioned above, this paper firstly elaborated the mechanism process of the coupling and coordination relationship between technological innovation and the ecological environment. After that, the paper chose the Pearl River Delta region as the study area. A comprehensive evaluation indicator system was constructed to evaluate the situation of technological innovation and ecological environment in the Pearl River Delta region from 2007 to 2018. Subsequently, we quantitatively calculated the coupling coordination level between technological innovation and ecological environment with the help of coupling coordination degree model of physics. What's more, the paper analyzed and discussed the spatiotemporal evolution characteristics of their coupling coordination development situation in the Pearl River Delta region. Our findings are as follows. Firstly, both the situation of technological innovation and ecological environment showed a gradual upgrade trend in all cities of the Pearl River Delta from 2007 to 2018. More importantly, the coupling degree and the coupling coordination degree between technological innovation and ecological environment also presented the positive characteristics that moved from low level state to more advanced state. As for spatial distribution, the coupling coordination degree between technological innovation and ecological environment in the Pearl River Delta region showed a significantly spatial pattern which descended from the core region to the periphery, meanwhile, Guangzhou, Shenzhen, Foshan and Dongguan such developed cities are situated in the central area. In terms of coupling and coordinated types, although most cities' technological innovative ability hindered the improvement of coupling coordination degree between technological innovation and the ecological environment after 2007, the innovation ability of cities has been continuously captured with the ecological environment which pushed the coupling coordination degree to reach the basic coordination or even advanced level as time goes on. However, the development of Zhaoqing was slow compared with other cities, and it still belonged to the basic imbalance-technological innovation hindered type during the study period. Therefore, under the guidance of regional high-quality development strategy, we concluded several developmental strategies for the Pearl River Delta to implement the coordinated and sustainable development of technological innovation and ecological environment, for example, improving ecological innovation by increasing investment in innovation factors, controlling pollutant emissions and reasonably maintaining ecological land.