To investigate the effect of polymerization ( n = 1, 2, 3, and 4) on the charge-transfer (CT) mechanisms in the one (two)-photon absorption (OPA and TPA) process of D-A-type triphenylamine derivatives, charge density difference is used to graphically represent the CT characteristics. A transition density matrix is utilized to reveal the direction of CT on different groups quantitatively. With the n increasing, electrons are mainly transferred between the groups in the middle position of the molecular chain during OPA and TPA processes. Simulated results show that the energy gap and excitation energy have a good linear relationship with the reciprocal of the polymerization degree. Importantly, the polymerization effect can effectively increase the electronic transmission capability, TPA performance, and second hyperpolarizability. Besides, the simplified sum over state model reveals the variation factor of the TPA cross-section and the second static hyperpolarizability. The McRae formula and Bakhshiev formula are used to estimate the difference of dipole moments, which is an important parameter of the second hyperpolarizability. The comprehensive analysis of the nonlinear optical (NLO) parameters of triphenylamine derivatives can provide some significant guidance for molecular design and improve the NLO performance of D-A molecular materials. Also, the thermodynamic parameters can provide some theoretical supports for solving practical problems.