Herein, different long alkyl chains (C1, C6, C12, and C16) were introduced as hydrophobic segments to enhance the performance of hydrogels reinforced by latex particles (LP-Gel). Poly(butyl acrylate) (PBA) latex particles (LPs) were employed as hydrophobic association cross-linking centers. First, the PBA latex particles were prepared via emulsion polymerization, and then, LP-Gel with high mechanical strength was prepared via one-pot free radical polymerization using acrylamide as a monomer, LP as a cross-linking center, and methacrylate as a hydrophobic molecule. It was found that the length of the hydrophobic alkyl chains from methacrylate has a significant effect on the mechanical performance and swelling degree of the hydrogels. The short alkyl chains exhibited weak hydrophobic interactions, and the resulting LP-Gel had a low mechanical strength. However, the long alkyl chains can effectively entangle with LPs through strong hydrophobic interactions, which significantly enhance the mechanical strength of the hydrogels. As a result, the LP-Gel exhibits a maximum fracture stress of 1.2 MPa and elongation of 2336%. This study will have a profound impact on the understanding of hydrogels toughened by hydrophobic alkyl chains of different lengths.