With the rapid development of textile technology, single‐function textile finishing is difficult to meet the current needs of people for textiles. Textiles with flame retardancy, superhydrophobicity, UV resistance, and other functions are increasingly favored by people. At present, most of the preparation processes of multifunctional textiles are complex and time‐consuming. In this work, a flame retardant hexamethylenediamine tetramethylene phosphate ammonium salt of hexamethylenediamine ‐ N, N, N′, N′ ‐ tetra (methylphosphonic acid) (AHDTMPA) was synthesized using hexamethylenediamine tetramethylene phosphate (HDTMPA) and urea with aqueous solution as solvent. Then AHDTMPA and cetyltrimethoxysilane were added into the solution with methyl trimethoxysilane (MTMOS) and tetraethyl orthosilicate (TEOS) as precursors to obtain a multifunctional sol. Finally, the multifunctional cotton fabric can be obtained by immersing the cotton fabric in the multifunctional sol in one‐step. The limiting oxygen index (LOI) and water contact angle (WCA) value of the finished cotton fabric was 27.6% and 131.4°, respectively. The FT‐IR characterization results and the SEM analysis verified the synthesis of AHDTMPA. The micro calorimeter combustion (MCC) and thermo gravimetric (TG) analysis indicated that the finished samples had less heat release capacity and less weight loss. The smoke density test showed good smoke suppression of the finished cotton fabric. Moreover, the whiteness of finished samples was nearly unchanged. In this work, the flame retardant and hydrophobic multi‐functional cotton fabric was prepared by one‐step, and the method is simple and efficient. The prepared functional cotton fabrics can be widely used in home textile fabrics, automotive interior fabrics, clothing fabrics, flags, tents, and protective clothing.