In this article, based on nonadiabatic molecular dynamics with electronic transitions, the elaborate ultrafast process of hot excitons in conjugated polymer solar cells is revealed. When an external optical beam/pulse with the intensity of 30 µJ/cm-2 is utilized to excite a conjugated polymer, just within only 50 fs, the electronic transition not only redistributes the electron population in the original molecular orbital, but also starts to localize the electron cloud of excited states and to distort the alternating bonds in the polymer chain. Up to 300 fs, the lattice distortion has been stabilized. During the formation of hot excitons, the prominent self-trapping effect of conjugated polymer triggers the occurrence of local infrared active phonon modes, with five peaks in the phonon spectrum as the hot excitons relax. The characteristic phonon spectrum and infrared modes hence form the fingerprint of the hot excitons of a conjugated polymer, which are readily distinguished from other excitation states in the polymer.