Orientation-dependent interactions can drive unusual self-assembly of colloidal particles. This study, based on combined epifluorescence microscopy and Monte Carlo simulations, shows that amphiphilic colloidal spheres, hydrophobic on one hemisphere and charged on the other, assemble in water into extended structures not formed by spheres of uniform surface chemical makeup. Small, compact clusters each comprised of less than 10 of these Janus spheres link up, as increasing salt concentration enhances electrostatic screening, into wormlike strings.