Flexible optoelectronics have fully demonstrated their transformative roles in various fields, but their fabrication and application have been limited by complex processes. Liquid metals (LMs) are promising to be ideal raw materials for making flexible optoelectronics due to their extraordinary fluidity and printability. Herein, we propose a painting-modifying strategy based on solution processability for directly printing out fluorescent flexible optoelectronics from LMs via surface modification. The LMs of eGaIn, which were obtained by the mixing of gallium with indium metal spheres, were used as ink to paint high-finesse patterns on flexible substrates. Through introducing surface modification of LMs, the gallium atom on the surface of the LMs was directly transformed into the composite fluorescent functional layers of GaO(OH) and GaN after being modified with an ammonia aqueous solution. Owing to painting, this strategy is not limited by any curved surfaces, shapes, or facilities and has excellent adaptability. Particularly, the fluorescent layers were obtained through a spontaneous, instantaneous, and solution-processable process that is environmentally friendly, easy to administrate, recyclable, and adjustable. The present finding breaks through the limitations of LMs in making flexible optoelectronics and provides strategies for addressing severe challenges facing existing materials and flexible optoelectronics. This method is expected to be very useful for fabricating flexible lights, transformable displays, intelligent anticounterfeiting devices, skin-inspired optoelectronics, and chameleon-biomimetic soft robots in the coming time.