NOVELTY - Tailoring work function of an electrode to a desired work function value, comprises: (a) selecting first functionalized semiconducting polymer (FSP); (b) coating an electrode with a first solution containing FSP and rinsing to form a first half bilayer; (c) measuring the work function of the first half bilayer; (d) comparing the first work function value to the desired work function value; (e) coating the first half bilayer with poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) to form a first bilayer; (f) measuring the work function of the first bilayer; and (g) repeating steps (a)-(f).    USE - The method is useful for tailoring the work function of an electrode to a desired work function value for use in an organic photovoltaic device (claimed).    ADVANTAGE - The method: selects FSps that are more likely to result in a desired work function value with a minimum number of half bilayers or bilayers; utilizes FSP which allows for efficient optimization of overall device design; and increases the thickness while maintaining the work function with respect to film uniformity.    DETAILED DESCRIPTION - Tailoring the work function of an electrode to a desired work function value, comprises: (a) selecting a first functionalized semiconducting polymer (FSP) for an electrode based on known work function values obtained from a library of established work function values for electrode/FSP pairs; (b) coating an electrode with a first solution containing FSP and rinsing to form a first half bilayer; (c) measuring the work function of the first half bilayer to obtain a first work function value; (d) comparing the first work function value to the desired work function value; (e) coating the first half bilayer with poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) to form a first bilayer; (f) measuring the work function of the first bilayer to obtain a first bilayer work function value; and (g) repeating steps (a)-(f) until the desired work function value is obtained. An INDEPENDENT CLAIM is also included for tailoring the work function of an electrode to a desired work function value, comprising: selecting a first small molecule for an electrode based on known work function values obtained from a library of established work function values for electrode/small molecule pairs; and steps (b)-(g) as per above per se.