In the mixed-valence manganites, a near-infrared laser typically melts the orbital and spin order simultaneously, corresponding to the photoinduced d 1 d 0 − → d 0 d 1 excitations in the Mott-Hubbard bands of manganese. Here, we use ultrafast methods -both femtosecond resonant x-ray diffraction and optical reflectivity -to demonstrate that the orbital response in the layered manganite Nd1−xSr1+xMnO4 (x = 2/3) does not follow this scheme. At the photoexcitation saturation fluence, the orbital order is only diminished by a few percent in the transient state. Instead of the typical d 1 d 0 − → d 0 d 1 transition, a near-infrared pump in this compound promotes a fundamentally distinct mechanism of charge transfer, the d 0 − → d 1 L, where L denotes a hole in the oxygen band. This novel finding may pave a new avenue for selectively manipulating specific types of order in complex materials of this class.