A novel magnetic field measurement method based on the magneto-volume effect is proposed. The magnetic field sensing structure fabricated by the proposed measurement method is made by the magnetic fluid (MF) partially filled into the hollow core fiber (HCF). The presence of air provides conditions for the change of MF volume with the magnetic field in the proposed sensing structure. Therefore, the magneto-volume effect is introduced into the magnetic field sensing mechanism. From 109.6 to 125.8 Gs, the peak wavelength shift is −65480 pm and the sensitivity is −4219.15 pm/Gs, which is 28.16 times higher than that of the fabricated contrast sensing structure. The sensitivity of the magnetic field sensing structure is greatly improved by introducing the magneto-volume effect compared with the contrast sensing structure. The response time and recovery time of the sensing structure are equally 0.2 s. Therefore, the sensing structure has high sensitivity, good linearity, and short response time, which has potential application prospects in magnetic field sensing.