Ramie (Boehmeria nivea) is believed to be one of the strongest natural fibers, but it still remains behind synthetic materials in terms of tensile strength. In this study, ramie materials were prepared to evaluate the modification crosslinking effect of natural fiber. The aim is to optimize various concentrations of citric acid (CA) crosslinking by adding Sodium hypophosphite (NaPO2H2), which is activated at different temperatures, to obtain the highest tensile mechanical strength. This crosslinking effect has been confirmed by FTIR to show the esterification process in the molecular structure of cellulose. The changes in the character of the fiber surface were analyzed by SEM. The tensile strength increased from 62.33 MPa for 0% CA to 124–172.86 MPa for decorticated fiber with a CA concentration of 0.75–1.875% (w/w). A significant increase in tensile strength was observed more than 19 times when CA/SHP 1% was treated at an activation temperature of 110 °C with a superior tensile strength of 1290.63. The fiber crosslinked with CA/SHP should be recommended for application of Natural Fiber Reinforced Polymer Composite (NFRPC), which has the potential to use in functional textile and industrial sector automotive or construction.