Requirements and regulations concerning the increased share of fuels derived from renewable sources are continually becoming more stringent. This constitutes an important motivation for research into alternative fuels applicable in compression-ignition engines. No studies isolating the effect of the first pilot injection (P1) timing angle alone on the combustion course of a rapeseed oil–n-hexane blend have so far been found in the literature. The aim of the study was a preliminary assessment of the effect of varying the start-of-injection angle of P1 on the combustion characteristics of a rapeseed oil blend containing 10% n-hexane (OR90Hex10). Particular attention was paid to isolating the effect of P1 alone on the combustion course. Tests were performed on a chassis dynamometer with a Fiat Qubo 1.3 Multijet (Euro 5), ECU maps modified via WinOLS, at 50 km/h with a load torque of 50 Nm. The start-of-injection angle of P1 was varied in the range from −4 to +4°CA relative to the nominal setting (°CA – crank angle degree). Settings of the second pilot injection and main injection remained unchanged. Each of the presented results was averaged over n = 100 engine operating cycles. The highest indicated pressure (pi = 0.999 MPa) occurred under nominal control; advancing P1 increased dp/dα and Qmax, retarding it reduced them. A retardation of +2°CA constituted a compromise solution. It reduced the maximum rate of pressure rise dp/dα by approximately 7.7% relative to the nominal injection-angle setting for OR90Hex10 (from 0.594 to 0.548 MPa/°CA). This was accompanied by a reduction in pi of 2.6–4.7% — from 0.999 MPa to the range of 0.952–0.973 MPa, obtained for injection-angle retardation corrections from +1 to +4°CA. The angle of maximum combustion pressure for the rapeseed oil–n-hexane blend, on the other hand, was α p max = 11.40°CA, 0.07°CA less than diesel fuel's 11.33°CA. The preliminary results indicate that adjusting the timing angle of P1 may constitute a useful calibration parameter for limiting the rate of combustion pressure rise in rapeseed oil–n-hexane blends; confirming this requires research over a broader range of engine operating points.