A multiphasic microfiber for a three-dimensional tissue scaffold and/or cellular support is provided in one aspect that includes at least one biocompatible material. The multiphasic microfiber optionally has a first phase and at least one distinct additional phase and is formed by electrohydrodynamic jetting. Further, such microfibers optionally have one or more biofunctional agents, which may be surface-bound moieties provided in spatial patterns. Multiphasic microfibers formed in accordance with the disclosure may form, in some cases, three-dimensional fiber scaffolds with precisely engineered, micrometer-scaled patterns for cellular contact guidance, which may thus support and/or promote cellular growth, proliferation, differentiation, repair, and/or regeneration for tissue and bioengineering applications.