The differences of residents' travel purpose, travel time and regional attribute will lead to the heterogeneity of travel behavior. Working days and holidays have completely different time attributes, and the travel purpose is quite different. Therefore, comparing them has become an important way to reveal the inter-city travel network from different perspectives. Using migration data inferred from passenger travels during working days in April (11-15 April, 2016) and National Day golden week (1-7 October, 2016) from Tencent Location Big Data, this paper made a comparison of the spatial structure of inter-city travel network during weekdays and holiday in China. The results are as follows: (1) The average daily inter-city residents' travel scale during the golden week was significantly higher than that during the weekdays, but the travel distance and network clustering degree were significantly lower than the latter. (2) The two networks form three types of cross-regional group, adjacent group and provincial group. During the golden week, the number of cross-regional groups is significantly lower compared with weekdays, the number of regional and local hub cities is more than that of weekdays, and the number of adjacent groups and provincial groups is significantly higher than that of weekdays. (3) On weekdays, the three major cities of Beijing, Shanghai and Guangzhou have a prominent core position, and the function of tourism and transportation hub is highlighted in the golden week. (4) Weekday intercity network to cross-regional links, and the golden week is showing a clear spatial proximity effect, and formed a provincial capital as the center, the provincial travel core-peripheral mode. The structure and difference of inter-city travel network in the two periods are influenced by many factors, including geographical proximity, administrative division (proximity of cultural system), travel distance and travel purpose.