Polyelectrolyte multilayers of cationic and anionic starch have been used to enhance the strength properties of paper. All starches used in this investigation had a degree of substitution around 0.065. Optical reflectometry showed that a combination of cationic and anionic starch could form polyelectrolyte multilayers onto silicon oxide surfaces. The same combination of starches was then applied to unbeaten, bleached softwood kraft fibres to form three layers, i.e. a cationic/anionic/cationic starch combination. The results showed a significant increase in the paper strength properties in terms of tensile index, strain at break, and Scott Bond. The adsorbed amount of starch in the sheets, determined using an enzymatic method, was found to increase with each successive starch treatment. The increased paper strength was not only due to the increase in adsorbed amount of starch; rather, the chemical composition of the starch was also important. Cationic starch with high amylose content had a more positive effect on the paper strength properties. Furthermore, it was observed that anionic starch, despite being adsorbed in large amounts, did not contribute to the increase in tensile strength or strain at break to the same extent as did cationic starch. However, the out-of-plane properties, measured as Scott Bond properties, increased with the adsorbed amount, regardless of the chemical composition of the starch used in the outermost layer