A series of vinyl versatate (VV10) modified poly(vinyl acetate) adhesive (HVPVAc) were prepared using soap-free emulsion polymerization. Attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy was used to characterize the structure of the modified poly(vinyl acetate) latex. The effect of the VV10 content on particle size, viscosity, mechanical properties, and T-peel strength of the modified poly(vinyl acetate) was determined. No absorption peak at 1675–1500 cm−1 in the ATR-FTIR spectrum was observed as a result of the carbon-carbon double bond reacting completely. With the occurrence of -C-O-C and the disappearance of the carbon-carbon double bond in the FTIR spectrum, a more complex structure formed. The structure improves the mechanical properties. Increasing the VV10 content resulted in an increase in particle size from 63 nm to 221 nm, a steady increase in the viscosity of the HVPVAc latex, an increase in tensile strength from 7 MPa to 13.4 MPa, and a decrease in breaking elongation from 1310% to 1004%. As the VV10 content increased from 0 to 30% by weight, the T-peel strength of the HVPVAc adhesive increased from 8.35 N/mm to 18.97 N/mm, indicating improved adhesive performance.