Polymer/surfactant composites have emerged as a subject of interest for their diverse applications. The improved solution properties in polymer/surfactant composites have been correlated to the formation of premicellar surfactant aggregate-polymer complexes (PS) at a surfactant concentration well below their critical micelle concentrations. Using different physicochemical and spectroscopic techniques here we have studied PS formed by hydroxypropyl cellulose, a nonionic-biocompatible polymer, and alkyl sulfate surfactants of different tail lengths. Our study shows that an increase in surfactant tail length eases PS formation and enhances PS-induced polymer cross-linking and, correspondingly, solution viscosity. PS consisting of shorter tail surfactants and those with longer tail surfactants differ microscopically as the former offers more polar interior than the later as evidenced from fluorescence measurements. Our study establishes that shorter tail surfactants intend to stay loosely packed inside PS and allow larger water penetration, which creates a relatively polar hydrophobic core compared to the PS with longer tail surfactants. The stronger packing of PS with longer tail surfactants is an outcome of favorable interaction between polymer polar groups and surfactant headgroups, which further creates strongly hydrogen-bonded water in their hydration shell.