For using 2,2′,7,7′-tetrakis(N,N′-di-p- methoxyphenylamine)-9,9′-spirobifluorene (spiro-OMeTAD) as a hole conductor in solar cells, it is necessary to improve its charge-transport properties through electrochemical doping. With the aim of fabricating efficient mesoscopic TiO2/CH3NH3PbI3 heterojunction solar cells, we used tris[2-(1H-pyrazol-1-yl)-4-tert- butylpyridine)cobalt(iii) tris(bis(trifluoromethylsulfonyl) imide)] (FK209) as a p-dopant for spiro-OMeTAD. The mixture of spiro-OMeTAD, FK209, lithium bis(trifluoromethylsulfonyl)imide (Li-TFSI), and 4-tert-butylpyridine (TBP) exhibited significantly higher performance than mixtures of pristine spiro-OMeTAD, spiro-OMeTAD, and FK209, and spiro-OMeTAD, Li-TFSI, and TBP. Such a synergistic effect between the Co-complex and Li-TFSI in conjunction with spiro-OMeTAD effectively improved the power conversion efficiency (PCE) of the fabricated solar cells. As a result, we achieved PCE of 10.4%, measured under standard solar conditions (AM 1.5G, 100 mW cm-2). © 2013 The Royal Society of Chemistry.