The networks comprising ETTMP, TEMPIC and TMPMP exhibit a visible glass transition temperature signified by an endothermal baseline shift, while no glass transition is observed when CHTT is used as a comonomer. Endothermal peaks signifying melting transitions confirm that we achieve crystallinity in all cases. To our knowledge, this was not achieved to date without the use of a chain extender in LC thiol-ene networks. Very high crystallinity is achieved using pure ETTMP as comonomer, as well as CHTT with smaller amounts of ETTMP. Use of TEMPIC and TMPMP results in much lower crystallinity.