Herein, the paper reports an experimental investigation lasting one year on the chloride resistance of polypropylene fiber (PF) reinforced concrete with fly ash (FA). Four influential factors at four levels were studied, viz. water to binder ratio (w/b) (0.53, 0.34, 0.29, and 0.25), PF dosage (0%, 0.06%, 0.08%, and 0.1% in volume basis of the total volume of concrete), FA content (0%, 15%, 25%, and 35% in mass substitution ratio of cement) and concentration of NaCl solution (0%, 3%, 5%, and 7%). Dry–wet cyclic immersion and long-term soaking were taken into consideration in addition to the aforementioned factors. A L16(44) orthogonal table was used to sequence influencing factors and to determine the optimal combination. Results showed that 7% NaCl solution caused the highest chloride content in 0–5 mm depth, whilst the w/b ratio of 0.25 curbed the chloride penetration within 10 mm even for concrete subjected to dry–wet cyclic immersion for 360 d. Subsequently, a respond surface model (RSM) basing on polynomials was constructed to visually evaluate the effect of PF dosage and FA content. Results clarified that a cubic model was more precise and PF dosage and FA content turned out to have the positive facilitation to chloride resistance. The positive effect of PF however is not consistent and commensurate for concrete with varied fly ash content. Finally, a fuzzy logic based nonlinear model accommodating all seven influencing factors was verified to be proper and adaptive in predicting chloride content.