In the process of global urban development, there are urgent ecological security and environmental pollution problems, green development is the fundamental way for urban sustainable development, economic transformation and mitigation of ecological and environmental problems. Based on the panel data of 283 cities at prefecture level and above in China from 2003 to 2017, this paper analyzes spatial–temporal evolution characteristics of urban green development efficiency (UGDE) and the peer effects of UGDE between cities of different grades. It is found that during the study period, in terms of temporal evolution, the average UGDE in China increased from 0.47 in 2003 to 0.61 in 2017, with a cumulative growth rate of 29.79%, showing a rising trend in general. In terms of spatial evolution, the number of low-efficiency cities and medium-efficiency cities continued to decrease. The eastern region has always been the main distribution area of higher-efficiency cities and high-efficiency cities; in the central region, UGDE in most cities improved significantly; in the western region, UGDE has always lagged behind that in the eastern and central regions. In addition, the center of gravity of UGDE presented a trend of northwest migration in general, with a total displacement of 100.07 km, and UGDE showed a spatial dispersion trend. The empirical results indicate that the improvement of UGDE in large cities has a driving effect on that in neighboring medium cities and small cities through the positive peer effect, and the growth of UGDE in medium cities has a promoting effect on that in neighboring small cities through the positive peer effect; the increase of UGDE in medium cities has a positive peer effect on that in neighboring large cities, and the growth of UGDE in small cities has a positive peer effect on that in neighboring medium cities; UGDE promotes each other between large cities through the positive peer effect.