The present paper provided not only a deep insight of network structures of borosilicate glasses but also a basic linkage between the network structures and the viscous flow behaviors of many borosilicate melts. The structures of a ternary system of CaO-SiO2-B2O3 were characterized using Fourier transformation infrared (FTIR), Raman, and magic angular spinning nuclear magnetic resonance spectroscopy. The results of FTIR and Raman spectra complementally verified that the main Si-related units were SiO4 tetrahedral with zero, one, two, and three bridging oxygens [Q0(Si), Q1(Si), Q2(Si), and Q3(Si)]; the added B2O3 leaded to an increase of Q3(Si) at the cost of Q0(Si) and Q2(Si), and therefore an increasing degree of polymerization (DOP) was induced. Additionally, the 11B NMR spectra demonstrated that the dominant B-related groups were BO3 trigonal and BO4 tetrahedral, while an increasing B2O3 content facilitated the existence of BO4 tetrahedral. Moreover, there was a competitive effect between the enhanced DOP and the presence of BO3 trigonal and BO4 tetrahedral in the networks, which therefore resulted in a decreasing viscosity of borosilicate melts in numerous studies.