The α-Ca2SiO4 and rocksalt-type (R) CaO condensates/particulates with an enhanced solid solution of P and Si + P ions, respectively, were produced via pulsed laser ablation of a silicocarnotite (Ca5(PO4)2SiO4) target under a relatively high peak power density of 1.8 × 109 Watt/cm2 in high vacuum (8 × 10–5 torr). The condensates were dispersed in an amorphous phase of Ca–Si–P–O linkage as spheres up to submicrons in size or coalesced in particulates by the {100}R, {111}R, and {1̅21̅0}α facets to follow a preferred crystallographic relationship of (1̅1̅1)R//(1̅21̅0)α; [101]R//[101̅1]α, with a fair three-dimensional match of the lattice planes. The 1-D commensurate superstructures n × (200)R and n × (1̅21̅0)a, where n = 1.5 and 3, were commonly noted for the condensates in the particulates. The P-doped α-Ca2SiO4 and (Si, P)-codoped CaO showed characteristic luminescence at 407 and 537 nm, respectively, under the combined influences of internal compressive stress as well as substitutional and/or interstitial defects with charge/volume-compensating cation vacancies for potential optoelectronic and photocatalytic applications.