A polymeric optical waveguide having a core and a cladding surrounding the core, wherein at least one of said core and cladding comprises a polymeric optical material which is prepared by cross-linking a polysiloxane comprising at least one unit selected from the group consisting of units A, B, C and D represented by formulae (II-1) to (II-4), respectively, and at least one unit selected from the group consisting of units E and F represented by formulae (II-5) and (II-6), respectively:
- ##STR42## wherein each of R.sub.3 to R.sub.13 is independently (a) an alkyl, deuterated alkyl or halogenated alkyl groups;
- or (b) a phenyl, deuterated phenyl or halogenated phenyl group, with a cross-linking agent which is capable of cross-linking said polysiloxane, and which cross-linking agent is selected from the group consisting of
- (a) a polyisocyanate selected from the group consisting of compounds of formulae which follow:
- ##STR43## and Si(NCO).sub.4, wherein each of R.sub.16, R.sub.17, and R.sub.18 is independently an alkylene group or a phenylene group and k is a positive integer, and a substituted form of any of the foregoing compounds in which at least one of the hydrogen atoms of the alkylene or phenylene group is substituted by at least one group selected from halogen or deuterium;
- (b) a silane compound selected from the group consisting of an acetoxysilane, an alkoxysilane, an ketoximesilane, an aminosilane, an aminoxysilane, an silazane and an amidosilane;
- (c) an alkoxide compound selected from the group consisting of compounds represented by Ti(OZ).sub.4, Zr(OZ).sub.4 and Al(OZ).sub.3, wherein Z is an alkyl or cycloalkyl group;
- and
- (d) a chelated compound selected from the group consisting of di-i-propoxy bis(acetylacetone)titanate, di-n-butoxy bis(triethanolamine)titanate, Zr tetraacetylacetonate, ethyl acetoacetatoaluminum diisopropylate and aluminum tris(ethylacetoacetate).