We investigate the use of bismuth ferrite (BFO) nanoparticles for tumor tissue labeling in combination with infrared multiphoton excitation at 1250 nm. We report the efficient and simultaneous generation of second- and third-harmonic signals by the nanoparticles. On this basis, we set up a novel imaging protocol based on the co-localization of the two harmonic signals and demonstrate its benefits in terms of increased selectivity against endogenous background sources in tissue samples. Finally, we discuss the use of BFO nanoparticles as mapping reference structures for correlative light–electron microscopy.