Increasing the number of imaging channels beyond the conventional three has been shown to be beneficial for a wide range of applications. However, it is mostly limited to imaging in a controlled environment, where the capture environment (illuminant) is known a priori. We propose here a novel system and methodology for multispectral imaging in an uncontrolled environment. Two images of a scene, a normal RGB and a filtered RGB are captured. The illuminant under which an image is captured is estimated using a chromagenic based algorithm, and the multispectral system is calibrated automatically using the estimated illuminant. A 6-band multispectral image of a scene is obtained from the two RGB images. The spectral reflectances of the scene are then estimated using an appropriate spectral estimation method. The proposed concept and methodology is generic one, as it is valid in whatever way we acquire the two images of a scene. A system that can acquire two images of a scene can be realized, for instance in two shots using a digital camera and a filter, or in a single shot using a stereo camera, or a custom color filter array design. Simulation experiments using a stereo camera based system confirms the effectiveness of the proposed method. This could be useful in many imaging applications and computer vision.