EDX and infrared photoluminescence (IR PL) analyses performed on erbium-doped porous silicon waveguides (PSWG) were studied using different doping conditions. Both parameters of the cathodisation electrochemical method used for Er incorporation and parameters of thermal treatments required for Er optical activation were taken into consideration. Firstly, by varying the current density and the time of cathodisation, we have shown that a current density of 0.1 mA/cm2 for 10 min allows homogeneous Er doping to be achieved throughout the depth of the guiding layer. Then, the PL intensity at 1.53 mm was studied as a function of the oxidation time at 900 °C and Er diffusion temperature for 60 min. Increasing the oxidation time up to 1 h allows PL to be enhanced due to active Si–O–Er complex formation whereas an oxidation time of 2 h induces a decrease in PL because of Er segregation. Moreover, an increase in the diffusion temperature induces an optimal distribution of optically active Si–Er–O complexes inside the crystallites. When the temperature is too high, a PSWG densification and Er segregation occurs inducing a decrease in PL due to energy transfer phenomena.