The work aims to provide theoretical basis for color protection of chilled meat by preparing the color protective fiber materials with the electrospinning technology. The electrospinning technology was used to mix the biodegradable PLA and NaNO2 having good color protection to prepare the color protective fiber. The effects of different process parameters on the morphology of the fibers were studied. According to the SEM results, the optimal conditions of fiber morphology were selected and NaNO2 was added to prepare the color protective fibers. The composition and hydrophilicity of the prepared fibers were analyzed through FT-IR and static contact angles, and the fiber release properties were also tested. It was found that, with the increase of collection distance and electrospinning speed, the average diameter of PLA fiber decreased; with the increase of voltage, the average diameter of polylactic acid fiber increased first and then decreased. Suitable spinning process parameters were obtained: voltage of 15 kV, spinning speed of 0.5 mL/h, and receiving distance of 25 cm. With the increase of NaNO2 content, the average diameter of polylactic acid sodium nitrite fiber decreased. With the addition of NaNO2, the effect on hydrophilicity of fiber was not obvious. When the content of NaNO2 increased, the release time prolonged, and the release rate of NaNO2 in the film was reduced. Polylactic acid sodium nitrite color-developing fiber is prepared by electrospinning technology, which has excellent sustained release effect and can be applied to color protective packaging of meat and meat products.