By excitation with CW laser the photoluminescence of the polyparaphenylene (PPP) has been measured. The crystallinity of the as-prepared polymer PPP is demonstrated by X-ray diffraction. The results indicate that the extrinsic luminescence is the broad red luminescence which peaks around 619.0nm and 728.1nm, whereas the Intrinsic luminescence has the sharp luminescence peaks which appear around 436.0nm and 466.0nm. The luminescence is mainly from non-crystalline region of PPP. The origin of the extrinsic luminescence is discussed.