The aims were to determine the efficiency and its temporal-spatial evolvement characteristics by using data envelopment analysis (DEA), Malmquist index and exploratory spatial data analysis (ESDA) in 20 main producing provinces of maize in China during an 11 years period (2005—2015). The results showed that the average value of scale efficiency, comprehensive and pure technical efficiency of maize production in the study areas were unproductive. The high comprehensive technical efficiency was positively correlated with production methods. With an annual decrement of 6.7% in total factor productivity, mainly due to the lack of effective application of the production technology. The difference of the comprehensive technical efficiency between the provinces was mainly affected by the mode of agricultural production (especially technology, etc.), the scale of operation and the proportion of agricultural production. The provinces with high efficiency had both higher technical efficiency and scale efficiency, while the difference between the technical efficiency and the scale efficiency was relatively large for the provinces with lower efficiency. Lack of regional application of advanced production technology led to the reduction of total factor productivity. Various input elements of maize production were unreasonable, which can all be saved by using advanced and applicable production mode. The comprehensive technical efficiency in study areas showed obvious spatial clustering, while the spatial clustering of similar efficiency was not strengthened during the past 11 years, which was weakened in some years, the spatial differences were also expanded in each area. There were significant positive correlations in the northern area and Huang-Huai-Hai area of China. Improving the effective use of regional applicable technology and scale of operation were keys to improve the production efficiency of maize. Simultaneously, optimizing the spatial layout in main producing provinces of maize to achieve the “H-H” types was essential to improve the efficiency and competitiveness of maize production in China.