A facile and inexpensive way to prepare self-crosslinkable poly(dimethylsiloxane) (PDMS) for superhydrophobic treatment of cotton fabrics is reported in the study. Through thiol-ene click reaction between mercaptopropyltrimethoxysilane (MPTMOS) and vinyl-containing poly(dimethylsiloxane) (VPDMS), PDMS-g-TMOS can be simply and quickly synthesized. The trimethoxysilane group of PDMS-g-TMOS can react with hydroxyl group on cotton fabric and other -Si(OCH3)3 groups. The synthesized polysiloxane (PDMS-g-TMOS) was identified by FT-IR and 1H-NMR. The morphology of the treated cotton fabric was observed by SEM and XPS was used to analyze the elemental composition on the surface of cotton fabric. The analysis results indicated that the surface was fully covered with PDMS. Due to the low surface energy of PDMS and the rough surfaces of cotton fabric, the optimized water contact angle (WCA) and sliding angle were respectively 154°±0.4° and 14°±0.5°, indicating superhydrophobicity. Moreover, water spray test (AATCC Test Method 22-2010) was also applied to evaluate the water repellency of treated cotton fabric and a score of 90 was assigned according to AATCC Test Method 22-2010. The durability of treated cotton fabric was tested by 50 laundering cycles. The resultant WCA barely decreased and the score of water spray test dropped from 90 to 80, showing the reasonable wash durability.