The preference of short-term debt financing and high cash holdings have changed gradually for the listed companies in China since the Split-Share Structure Reform. Meanwhile, long-term debt plays a more important role in external financing than before. More specifically, the term mismatching of debt and asset have existed for a long time in China, which therefore increases the weight of long-term debt and will improve this situation and reduce mismatching risk. Besides that, based on the prior literature, cash holdings are crucial to preventing liquidity risk when long-term debt comes due, which requires a higher efficiency in capital turnover. The previous studies about debt maturity structure in China mainly distinguish long-term debt from short-term debt. They actually ignore the heterogeneity of long-term debt with different maturities. Thus, it is necessary to further research the trend of long-term debt maturity structure as well as the impact of long-term debt maturity structure on cash holdings. This paper manually collects the data of long-term debt maturity structure, and conducts an empirical research based on 2002—2014 data of Chinese A-share nonfinancial companies which were listed before 2002. Before we do empirical tests, it is important to account for the likelihood that cash holdings and long-term debt maturity structure are endogenously determined. Thus, we use Two-stage Least Squares (2SLS) to investigate the relationship between long-term debt maturity structure and cash holdings, including the impact of Split-Share Structure Reform on this relationship. The empirical results show that the weight of long-term debt due after three years has increased monotonously from 23.88% to 30.56% between 2002 to 2004 and 2011 to 2014. This phenomenon is conducive to matching the maturity of asset and liability. Meanwhile, the ratio of long-term debt to asset has increased from 5.39% to 11.09% between 2002 to 2004 and 2011 to 2014, and is close to the level of developed counties. We also find that firms with larger scale of long-term debt due within three years tend to have larger scale of cash holdings to hedge the liquidity risk. The estimate indicates that, after excluding the extreme impact of financial crisis in 2007—2009, a 1% increase in the fraction of long-term debt due within three years has led to a 4.721% increase in cash holdings. After the Split-Share Structure Reform, however, the sensitivity between long-term debt due within three-year and cash holdings has significantly decreased. This is because, as the prior literature put it, the tunneling problem and controlling shareholders opportunism before the Split-Share Structure Reform led to high cash holdings and high short-term debt (phenomenon of ′two high′) which resulted in a large coefficient of long-term debt due within three-year and cash holdings. After the Split-Share Structure Reform, the deficiencies of corporate governance relief and the coefficient of long-term debt due within three-year and cash holdings falls back to the normal level which faithfully reflects the impact of liquidity risk. The estimate indicates that the coefficient decreased from 8.246 before the Split-Share Structure Reform to 4.893 after that reform. Our findings provide a more detailed empirical result about long-term debt maturity structure of listed companies in China, and also imply that the Split-Share Structure Reform has made great contributions to listed companies in China in respect of debt maturity selection and capital turnover efficiency.