Since the rigidity and brittleness of PET-ITO electrodes limits the performance and development of flexible ECDs, the work aims to improve them with high conductivity silver nanowires (AgNWs). Therefore, the PANI ink was prepared by emulsion polymerization, and the ITO-free fully printed PET-PVA-AgNWs-PANI ECDs were prepared based on three processes, namely screen printing, spray printing, and coating printing, with the help of the bifunctionality of the PVA film (adhesive and insulating properties). The PET-PVA-AgNWs-PANI electrode with composite PVA prepared by printing had good electrical performance and stability (square resistance stably maintained below 10 Ω/sq). The ECDs based on PET-PVA-AgNWs-PANI also featured 48.04% visible light modulation and certain infrared light modulation. The ITO-free multicolor electrochromic devices prepared on the basis of printing have good flexibility and color change performance, which can be used widely in the scenarios of smart packaging and smart windows.