We report the use of solution-processed thin-film organic photodiodes for microscale chemiluminescence. The active layer of the photodiodes comprised a 1: 1 blend by weight of the conjugated polymer poly(3-hexylthiophene) [P3HT] and [6,6]-phenyl-C61-butyric acid-methylester [PCBM] - a soluble derivative of C60. The devices had an active area of 1 mm × 1 mm, and a broad-band response from 350 to 700 nm, with an external quantum efficiency of more than 50% between 450 and 550 nm. The photodiodes have a simple layered structure that permits facile integration with planar chip-based systems. To evaluate the suitability of the organic devices as integrated detectors for microscale chemiluminescence, a peroxyoxalate based chemiluminescence reaction (PO-CL) was monitored within a poly(dimethyl- siloxane) (PDMS) microfluidic device. Quantitation of hydrogen peroxide indicated excellent linearity and yielded a detection limit of 10 μM, comparable with previously reported results using micromachined silicon microfluidic chips with integrated silicon photodiodes. The combination of organic photodiodes with PDMS microfluidic chips offers a means of creating compact, sensitive and potentially low-cost microscale CL devices with wide-ranging applications in chemical and biological analysis and clinical diagnostics. © The Royal Society of Chemistry.