As a result, high-throughput experimental and computational methodologies are fostered to leverage their inherently high exploratory paces and accelerate novel materials discovery. In this review, we present some of the computational (pre)screening approaches performed prior to experimentation to select the most promising molecular candidates from the available materials libraries or, alternatively, generate molecules beyond human intuition. Then, we outline the main high-throuhgput experimental screening and characterization approaches with application in organic solar cells, namely those based on lateral parametric gradients (measuring-intensive) and on automated device prototyping (fabrication-intensive). In both cases, experimental datasets are generated at unbeatable paces, which notably enhance big data readiness. Herein, machine-learning algorithms find a rewarding application niche to retrieve quantitative structure–activity relationships and extract molecular design rationale, which are expected to keep the material's discovery pace up in organic photovoltaics.