All-optical ultrasound transducers are promising for imaging applications in minimally invasive surgery. In these devices, ultrasound is transmitted and received through laser modulation, and they can be readily miniaturized using optical fibers for light delivery. Here, we report optical ultrasound transmitters fabricated by electrospinning an absorbing polymer composite directly onto the end-face of optical fibers. The composite coating consisting of an aqueous dispersion of multi-walled carbon nanotubes (MWCNTs) in polyvinyl alcohol was directly electrospun onto the cleaved surface of a multimode optical fiber and subsequently dip-coated with polydimethylsiloxane (PDMS). This formed a uniform nanofibrous absorbing mesh over the optical fiber end-face wherein the constituent MWCNTs were aligned preferentially along individual nanofibers. Infiltration of the PDMS through this nanofibrous mesh onto the underlying substrate was observed and the resulting composites exhibited high optical absorption (>97%). Thickness control from 2.3 μm to 41.4 μm was obtained by varying the electrospinning time. Under laser excitation with 11 μJ pulse energy, ultrasound pressures of 1.59 MPa were achieved at 1.5 mm from the coatings. On comparing the electrospun ultrasound transmitters with a dip-coated reference fabricated using the same constituent materials and possessing identical optical absorption, a five-fold increase in the generated pressure and wider bandwidth was observed. The electrospun transmitters exhibited high optical absorption, good elastomer infiltration, and ultrasound generation capability in the range of pressures used for clinical pulse-echo imaging. All-optical ultrasound probes with such transmitters fabricated by electrospinning could be well-suited for incorporation into catheters and needles for diagnostics and therapeutic applications.