A colorimetric cellulose acetate (CA) membrane incorporated with Perilla frutescens (L.) Britt. anthocyanins (PFA) and chamomile essential oil (CO) is developed via electrospinning technique for food freshness monitoring and shelf-life extending. The moieties of PFA and CO are well-dispersed in fiber matrix by hydrogen bonds and their incorporation increases the fiber size but with no obvious influence on the fiber morphology at incorporation levels. The presence of CO enhances membrane hydrophobicity. The target membrane of CA-PFA6-CO15 (PFA6%, CO15%) has a wide color change range of pH 2–12 which is high sensitive and reversible towards external pH-stimuli. The membrane has good antibacterial activity against E. coli and S. aureus besides antioxidant activity. The release of bioactive moieties is predominantly controlled by Fickian diffusion. The target membrane can simultaneously monitor pork freshness in real-time and double the shelf-life at 25 °C, indicating its potential application in active and intelligent food packaging.